Technical Field
[0001] The present invention relates to a flame-retardant epoxy resin composition, a molded
article thereof and an electronic part.
Background Art
[0002] Epoxy resin has been widely used as insulating materials of electrical and electronic
parts such as a laminate material and an encapsulating material for a semiconductor
device, for example, IC, LSI, VLSI or the like because of excellencies in electrical
characteristics such as insulating property, heat resistance, moisture resistance,
acid resistance, solvent resistance, adhesiveness, mechanical properties, dimensional
stability and others, and furthermore, relative inexpensiveness.
[0003] In company with great development in the electronic technology in recent years, a
progress toward high integration in a semiconductor device and a laminate has reached
to higher level and at the same time, requirements for higher reliability thereof
have been increased. In such a current situation, epoxy resin used as an insulating
material has also been required to have better characteristics thereof such as heat
resistance (including soldering heat resistance), a flame retardance, moisture resistance,
adhesiveness arid mechanical properties.
[0005] Phosphazene compounds disclosed in the prior arts all lack a sufficient effect in
an aspect of improving moisture resistance of epoxy resin. Moisture resistance of
epoxy resin is an especially important property in a case where the resin is used
as material of a printed circuit board. That is, since laminates have a chance to
be used in the air with a high frequency and an insulating property and, hence, a
reliability are degraded due to moisture absorption, the resin is desired to have
a low water absorption and no change in electrical characteristics such as an insulating
property. In a case where a phosphazene compound low in effect of improving moisture
resistance is used as a laminate material, inconveniences such as swelling or peeling
of a metal sheet, a metal foil or the like occurs due to moisture absorption in a
high temperature treatment such as a soldering process, thereby disabling a laminate
with a long term reliability to be obtained.
DISCLOSURE OF THE INVENTION
[0006] The present inventors have conducted serious studies in order to solve the above
problem, which, as a result of the studies, leads to a discovery that epoxy resin
compounded with a specific phosphazene compound can exert conspicuously excellent
performance, thereby having completed the present invention.
[0007] That is, according to the present invention, there is provided a flame-retardant
epoxy resin composition containing an epoxy resin (A), a phosphazene compound (B)
and an epoxy hardener (C) wherein the component (B) is included in the range of 0.01
to 70 % by weight relative to a total quantity of the component (A) and the component(B),
and
wherein the component (B) is at least one member selected from the group consisting
of
- (1) a cyclic and/or a chain phosphazene compound expressed by a general formula (1):
wherein each R1 and R2, being identical or different, is an alkyl group having 1 to 18 carbon atoms, a cycloalkyl
group having 5 to 8 carbon atoms, an aryl group having 6 to 14 carbon atoms, an alkylaryl
group having 7 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an
alkenylaryl group having 8 to 18 carbon atoms, an amino group-substituted phenyl group,
an aminoalkyl group-substituted phenyl group where the aminoalkyl group has 1 to 6
carbon atoms, a hydroxy group-substituted phenyl group, a hydroxyalkyl group-substituted
phenyl group where the hydroxyalkyl group has 1 to 6 carbon atoms, a glycidyloxy group-substituted
phenyl group or a glycidyloxyalkyl group-substituted phenyl group where the glycidyloxyalkyl
group has 4 to 9 carbon atoms, providing that at least one of n R1s and n R2s is the glycidyloxy group-substituted phenyl group or the glycidyloxyalkyl group-substituted
phenyl group where the glycidyloxyalkyl group has 4 to 9 carbon atoms, and n indicates
an integer of from 3 to 10000;
- (2) a polymer of the cyclic and/or the chain phosphazene compound; and
- (3) a reaction product of the cyclic and/or the chain phosphazene compound with at
least one compound selected from the group consisting of an epoxy compound, a phenol
compound, an amine compound and an acid anhydride.
[0008] In the flame-retardant epoxy resin composition the component (B) and the component
(C) are included in the range of 0.01 to 70 % by weight and up to 70 % by weight,
respectively, relative to a total quantity of the component (A), the component(B)
and the component (C).
[0009] Furthermore, according to the present invention, there is provided a flame-retardant
epoxy resin composition containing an epoxy resin (A), a phosphazene compound (B),
an epoxy hardener (C) and an inorganic filler (D), wherein the component (B) and the
component (C) are included in the range of 0.01 to 70 % by weight and up to 70 % by
weight, respectively, relative to a total quantity of the component (A), the component(B)
and the component (C), and the component (D) is included up to 95 % by weight relative
to a total quantity of the component (A), the component(B), the component (C) and
the component (D) and
wherein the component (B) is at least one member selected from the group consisting
of
- (1) a cyclic and a chain phosphazene compound expressed by a general formula (1):
wherein each R1 and R2, being identical or different, is an alkyl group having 1 to 18 carbon atoms, a cycloalkyl
group having 5 to 8 carbon atoms, an aryl group having 6 to 14 carbon atoms, an alkylaryl
group having 7 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an
alkenylaryl group having 8 to 18 carbon atoms, an amino group-substituted phenyl group,
an aminoalkyl group-substituted phenyl group where the aminoalkyl group has 1 to 6
carbon atoms, a hydroxy group-substituted phenyl group, a hydroxyalkyl group-substituted
phenyl group where the hydroxyalkyl group has 1 to 6 carbon atoms, a glycidyloxy group-substituted
phenyl group or a glycidyloxyalkyl group-substituted phenyl group where the glycidyloxyalkyl
group has 4 to 9 carbon atoms, providing that at least one of n R1s and n R2s is the glycidyloxy group-substituted phenyl group or the glycidyloxyalkyl group-substituted
phenyl group where the glycidyloxyalkyl group has 4 to 9 carbon atoms, and n indicates
an integer of from 3 to 10000;
- (2) a polymer of the cyclic and/or the chain phosphazene compound; and
- (3) a reaction product of the cyclic and/or the chain phosphazene compound with at
least one compound selected from the group consisting of an epoxy compound, a phenol
compound, an amine compound and an acid anhydride.
[0010] A phosphazene compound of the component (B) used in the present invention is good
in reactivity and compatibility with an epoxy resin and considered to act as a hardener
and a flame retardant for the epoxy resin. This compound does not degrade electrical
characteristics such as an insulating property, mechanical properties, adhesiveness
and others of the epoxy resin, rather exerts excellent performance to improve the
characteristics and properties according to a case. A high reliability is therefore
shown and also sustained over a long time by a molded article (a molded product) obtained
by molding a flame-retardant epoxy resin composition of the present invention, for
example an electronic part such as a laminate.
BEST MODE FOR CARRYING OUT THE INVENTION
[0011] Description will be given for components used in the present invention below. Note
that the term of a "polymer" used in this specification includes an oligomer.
Component (A): epoxy resins
[0012] As epoxy resins, there can be exemplified the following epoxy resins commonly used
in the electrical and electronic fields: for example, novolak epoxy resin obtained
by a reaction between phenols and aldehydes, such as phenol novolak epoxy resin, brominated
phenol novolak epoxy resin, orthocresol novolak epoxy resin or naphthol novolak epoxy
resin; phenol epoxy resin obtained by a reaction between a phenol and epichlorohydrin,
such as bisphenol-A epoxy resin, brominated bisphenol-A epoxy resin, bisphenol-F epoxy
resin, bisphenol-AD epoxy resin, bisphenol-S epoxy resin, biphenol epoxy resin, alkyl-substituted
biphenol epoxy resin or tris(hydroxyphenyl) methane; aliphatic epoxy resin obtained
by a reaction between an alcohol and epichlorohydrin, such as trimethylol propane,
oligopropylene glycol or hydrogenated bisphenol-A; glycidyl ester epoxy resin obtained
by a reaction between hexahydrophthalic acid, tetrahydrophthalic acid or phthalic
acid and epichlorohydrin or 2-methyl epichlorohydrin; glycidyl amine epoxy resin obtained
by a reaction between an amine such as diaminodiphenyl methane or amino phenol and
epichlorohydrin; heterocyclic epoxy resin obtained by a reaction between a polyamine
such as isocyanuric acid and epichlorohydrin; and modified compounds of the above
epoxy resins. Among them, preferable are phenol novolak epoxy resin, orthocresol novolak
epoxy resin, bisphenol-A epoxy resin, biphenol epoxy resin, phenol epoxy resin obtained
by a reaction between tris(hydroxyphenyl) methane and epichlorohydrin and others.
The epoxy resins can be used singly or in a combination of two or more thereof.
Component (B): phosphazene compounds
[0013] A phosphazene compound used as a component (B) of the present invention is at least
one member selected from the group consisting of
- (1) a cyclic and/or a chain phosphazene compound expressed by a general formula (1):
wherein each R1 and R2, being identical or different, is an alkyl group having 1 to 18 carbon atoms, a cycloalkyl
group having 5 to 8 carbon atoms, an aryl group having 6 to 14 carbon atoms, an alkylaryl
group having 7 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an
alkenylaryl group having 8 to 18 carbon atoms, an amino group-substituted phenyl group,
an aminoalkyl group-substituted phenyl group where the aminoalkyl group has 1 to 6
carbon atoms, a hydroxy group-substituted phenyl group, a hydroxyalkyl group-substituted
phenyl group where the hydroxyalkyl group has 1 to 6 carbon atoms, a glycidyloxy group-substituted
phenyl group or a glycidyloxyalkyl group-substituted phenyl group where the glycidyloxyalkyl
group has 4 to 9 carbon atoms, providing that at least one of n R1s and n R2s is additionally the glycidyloxy group-substituted phenyl group or the glycidyloxyalkyl
group-substituted phenyl group where the glycidyloxyalkyl group has 4 to 9 carbon
atoms, and n indicates an integer of from 3 to 10000;
- (2) a phosphazene polymer obtained by polymerization of the cyclic and/or the chain
phosphazene compound; and
- (3) a reaction product of the cyclic and/or the chain phosphazene compound with at
least one compound selected from the group consisting of an epoxy compound, a phenol
compound, an amine compound and an acid anhydride.
[0014] The phosphazene compounds can be used singly or in a combination of two or more thereof.
[0015] The amino group-substituted phenyl group selectable as a substituent indicated by
R
1 and R
2 is a group obtained by substituting 1 to 5 amino and/or aminoalkyl groups at any
carbon atom or atoms on a benzene ring. This applies to the aminoalkyl group-substituted
phenyl group where the aminoalkyl group has 1 to 6 carbon atoms, the hydroxy group-substituted
phenyl group, the hydroxyalkyl group-substituted phenyl group where the hydroxyalkyl
group has 1 to 6 carbon atoms, the glycidyloxy group-substituted phenyl group and
the glycidyloxyalkyl group-substituted phenyl group where the glycidyloxyalkyl group
has 4 to 9 carbon atoms in a similar manner.
[0016] Note that an alkali metal salt described hereinafter means a potassium salt, a sodium
salt, a lithium salt or the like.
[Amino Phosphazene Compound (1a)]
[0017] An amino phosphazene compound (1a) that is a phosphazene compound (1) in which one
of n R
1s and n R
2s is additionally an amino group-substituted phenyl group and/or an aminoalkyl group-substituted
phenyl group is obtained according to a known prior method, for example, in which
an alkali metal salt of nitrophenol and/or nitroalkyl phenol and phosphonitrile chloride
are reacted with each other to produce nitrophenoxy phosphazene or nitroalkylphenoxy
phosphazene and then, hydrazine or hydrazine hydrate is used to reduce a nitro group
thereof to an amino group in the presence of a catalyst with a halide of a metal selected
from the group consisting of chromium, manganese, iron, cobalt, nickel, zinc and tin,
or a sulfate carried on active charcoal. Furthermore, there can be adopted a catalytic
hydrogenation method using a Raney nickel catalyst described in Inorganic Chemistry,
6(2), 394, 1967 and a known lithium aluminum hydride reduction method or a known boron
hydride reduction method.
[0018] Furthermore, in the reaction of an alkali metal salt of nitrophenol and/or nitroalkyl
phenol and phosphonitrile chloride with each other, there can be included, as a reactant,
at least one selected from the group consisting of alcohol compounds expressed by
R
3OM (in the formula, R
3 indicates an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group having 5
to 8 carbon atoms, an alkylaryl group having 7 to 18 carbon atoms or an alkenyl group
having 2 to 18 carbon atoms; and M indicates lithium, sodium or potassium) and phenol
compounds expressed by R
4OM (in the formula, R
4 indicates an aryl group having 6 to 14 carbon atoms or an alkenylaryl group having
8 to 18 carbon atoms and M indicates lithium, sodium or potassium). Thereby, there
are obtained aminophosphazene compounds (1a) each having plural amino and/or aminoalkyl
group-substituted phenol groups as substitutes.
[0019] As nitrophenols and nitroalkyl phenols, there are named, for example, 3-nitrophenol,
4-nitrophenol, 4-nitromethyl phenol, 4-nitroethyl phenol, 4-nitrobutyl phenol and
others.
[0020] As alcohol compounds and phenol compounds, there are named, for example, alkali metal
salts of methanol, ethanol, n-propanol, allylalcohol, isopropanol, n-butanol, n-octanol,
2,2,2-trifluoroethanol, 2,2,3,3,4,4,5,5-octafluoropentyl alcohol, phenol, 4-methyl
phenol, 4-ethyl phenol, 1-naphtol, 2-natphthol, 4-allyl phenol, 4-chlorophenol, 4-trifluoromethyl
phenol and others and sodium phenolate or sodium 4-methyl phenolate is preferable
in terms of heat resistance.
[0021] As concrete examples of aminophosphazene compounds (1a), there can be named, for
example, cyclotriphosphazenes with an aminophenoxy group and a phenoxy group as substitutes
in a mixed manner such as aminophenoxypentaphenoxycyclotriphosphazene, di(aminophenoxy)-tetraphenoxycyclotriphosphazene,
tri(aminophenoxy)-triphenoxycyclotriphosphazene, tetra(aminophenoxy)-diphenoxycyclotriphosphazene,
penta(aminophenoxy)-phenoxycyclotriphosphazene, and hexaaminophenoxycyclotriphosphazene;
cyclotriphosphazenes with an aminomethylphenoxy group and a phenoxy group as substitutes
in a mixed manner such as aminomethylphenoxy-pentaphenoxycyclotriphosphazene,
di(aminomethylphenoxy)-tetraphenoxycyclotriphosphazene,
tri(aminomethylphenoxy)-triphenoxycyclotriphosphazene,
tetra(aminomethylphenoxy)-diphenoxycyclotriphosphazene,
penta(aminomethylphenoxy)-phenoxycyclotriphosphazene, and
hexaaminomethylphenoxy cyclotriphosphazene; cyclotriphosphazenes with an aminoethylphenoxy
group and a phenoxy group as substitutes in a mixed manner such as aminoethylphenoxy-pentaphenoxycyclotriphosphazene,
di(aminoethylphenoxy)-tetraphenoxycyclotriphosphazene,
tri(aminoethylphenoxy)-triphenoxycyclotriphosphazene,
tetra(aminoethylphenoxy)-diphenoxycyclotriphosphazene,
penta(aminoethylphenoxy)-phenoxycyclotriphosphazene, and
hexaaminoethylphenoxy cyclotriphosphazene; cyclotriphosphazenes with an aminobutylphenoxy
group and a phenoxy group as substitutes in a mixed manner such as aminobutylphenoxy-pentaphenoxycyclotriphosphazene,
di(aminobutylphenoxy)-tetraphenoxycyclotriphosphazene,
tri(aminobutylphenoxy)-triphenoxycyclotriphosphazene,
tetra(aminobutylphenoxy)-diphenoxycyclotriphosphazene,
penta(aminobutylphenoxy)-phenoxycyclotriphosphazene, and
hexaaminobutylphenoxy-cyclotriphosphazene; and others.
[0022] Furthermore, there are named cyclotriphosphazenes with an aminoethylphenoxy group,
and an octyloxy group, trifluoroethoxy group, an octafluoropentyloxy group, an ethylphenoxy
group, a naphthyloxy group, an allyloxy group, a chlorophenoxy group or a trifluoromethylphenoxy
group as substitutes in a mixed manner.
[0023] Furthermore, there are named cyclotetraphosphazene, cyclopentaphosphazene, cyclohexaphosphazene,
a cyclophosphazene mixture (a mixture of cyclophosphazenes of the general formula
(1) with n being 3 to 15), a linear phosphazene mixture (a mixture of linear phosphazenes
of the general formula (1) with n being 3000 on average) and a cyclic (=cyclo) and
linear phosphazene mixture (a mixture of cyclic and linear phosphazenes of the general
formula (1) with n = 1000 on average) each with an aminophenoxy group and a phenoxy
group as substitutes in a mixed manner.
[0024] Furthermore, there are named cyclotetraphosphazene, cyclopentaphosphazene, cyclohexaphosphazene,
a cyclophosphazene mixture (a mixture of cyclophosphazenes of the general formula
(1) with n being 3 to 15), a linear phosphazene mixture (a mixture of linear phosphazenes
of the general formula (1) with n = 3000 on average) and a cyclic (=cyclo) and linear
phosphazene mixture (a mixture of cyclic and linear phosphazenes of the general formula
(1) with n = 1000 on average) each with an aminoethylphenoxy group and a phenoxy group
as substitutes in a mixed manner. The aminophosphazene compounds may include mixtures
of compounds with two or more types of substituents.
[0025] Among the above aminophosphazenes (1a), preferable are, for example, hexaaminophenoxycyclotriphosphazene;
hexaaminoethylphenoxycyclotriphosphazene; a cyclotriphosphazene with an aminophenoxy
group and a phenoxy group as substitutes in a mixed manner; a cyclotriphosphazene
with an aminoethylphenoxy group and a phenoxy group as substitutes in a mixed manner;
a cyclophosphazene mixture (a mixture of cyclophosphazenes of the general formula
(1) with n being 3 to 15) with an aminophenoxy group and a phenoxy group as substitutes
in a mixed manner; a linear phosphazene mixture (a mixture of linear phosphazenes
of the general formula (1) with n = 3000 on average) with an aminoethylphenoxy group
and a phenoxy group as substitutes in a mixed manner and especially preferable are
a cyclophosphazene mixture (a mixture of cyclophosphazenes of the general formula
(1) with n being 3 to 15) with an aminophenoxy group and a phenoxy group as substitutes
in a mixed manner and a linear phosphazene mixture (a mixture of linear phosphazenes
of the general formula (1) with n = 3000 on average) with an aminoethylphenoxy group
and a phenoxy group as substitutes in a mixed manner.
[Hydroxy Phosphazene Compound (1b)]
[0026] A hydroxy phosphazene compound (1b) that is a phosphazene compound (1) in which one
of n R
1s and n R
2s is additionally a hydroxy group-substituted phenyl group and/or a hydroxyalkyl group-substituted
phenyl group can be obtained according to known methods described in articles and
a patent publication; for example,
Masaaki YOKOYAMA, et.al.,; Journal of the Chemical Society of Japan. Industrial chemistry,
Vol. 67, No. 9, p. 1378 (1964),
Tomoya OKUBASHI, et.al.,; Journal of the Chemical Society of Japan. Industrial chemistry,
Vol. 73, No. 6, p. 1164 (1970),
Japanese Unexamined Patent Publication No. Sho-58-219190,
Alessandro Medici, et. al., Macromolecules, Vol. 25, No. 10, p. 2569 (1992) and others. That is, an alkali metal salt of 4-methoxyphenol or 4-(benzyloxy)phenol
in which one hydroxyl group of bivalent phenol is protected by a methyl group or benzyl
group and phosphonitrile chloride (
Japanese Unexamined Patent Publication No. Sho-54-145394,
Japanese Unexamined Patent Publication No. Sho-54-145395 and others) are reacted with each other and thereafter, a reaction with pyridine
hydrogen halide salt or boron trifluoride is performed to change a methyl group or
a benzyl group serving as deprotection to a hydroxyl group, thus enabling production
of hydroxyphenoxy phosphazene.
[0027] Furthermore, a hydroxy phosphazene compound (1b) can also be produced by a reaction
of an alkali meal salt of a hydroxyalkyl phenol such as 2-hydroxymethyl phenol, 3-hydroxymethyl
phenol, 4-hydroxymethyl phenol, 4-hydroxyethyl phenol and 4-hydroxybutyl phenol with
phosphonitrile chloride.
[0028] A hydroxy phosphazene compound (1b) in which plural ones of n R
1s and n R2s are hydroxy groups and/or hydroxyalkyl groups is produced only by using
at least one selected from the group consisting of alcohol compounds expressed by
a formula of R
3OM (in the formula, R
3 and M are the same as those of an aminophosphazene compound (1a) described above)
and phenol compounds expressed by a formula of R
4OM (in the formula, R
4 and M are the same as those of an aminophosphazene compound (1a) described above)
together in a reaction between an alkali metal salt of 4-methoxyphenol, or 4-(benzyloxy)phenol
in which one hydroxyl group of dihydric phenol is protected by a methyl group or benzyl
group and/or an alkali metal salt of a hydroxyalkyl phenol described above, and phosphonitrile
chloride.
[0029] As examples of compounds in which one hydroxyl group of dihydric phenol is protected
by a methyl group or benzyl group, there are named 4-methoxyphenol, 3-methoxyphenol,
2-methoxyphenol, 4-(benzyloxy)phenol and others.
[0030] In order to obtain a compound in which all of chlorine atoms of phosphonitrile chloride
are substituted with methoxyphenoxy and/or 4-(benzyloxy)phenoxy, a phosphonitrile
chloride solution is added to a solution of an alkali metal salt of methoxyphenol
or 4-(benzyloxy)phenol to cause a reaction therebetween. This reaction is preferably
performed in an organic solvent such as benzene, toluene, xylene, ether, tetrahydrofuran
or the like at room temperature for a time of from 1 to 20 hours, followed by the
reaction at a reflux temperature of a solvent in use for a time of about 1 to 3 hours
for completion thereof. On the other hand, in order to obtain a compound in which
part of chlorine atoms of phosphonitrile chloride is substituted with a methoxyphenoxy
group and/or a benzylphenoxy group, a solution of an alkali metal salt of methoxyphenol
or 4-(benzyloxy)phenol prepared quantitatively so as to leave the other part of chlorine
atoms of phosphonitrile chloride unsubstituted during the reaction is added to a phosphonitrile
chloride solution with a preferable result. By substituting unsubstituted chlorine
atoms of partially substituted phosphonitrile chloride with an alkali metal salt of
an alcohol or phenol compound described above, there can be obtained a compound with
a methoxyphenoxy or 4-(benzyloxy)phenoxy group and R
3O-group and/or R
4O-group (R
3 and R
4 are the same as those in an aminophosphazene compound (1a) described above) as substitutes
in a mixed manner. The reaction is preferably caused in conditions of a temperature
from room temperature to a reflux temperature or lower of a solvent in use and a time
ranging about 3 to about 8 hours. Note that, in this case, a method can be adopted
in which a mixed solution of an alkali metal salt of methoxyphenol or 4-(benzyloxy)phenol
and an alkali metal salt of alcohol or phenol compound is prepared in advance and
a phosphonitrile halide solution is added dropwise to the mixed solution to cause
a reaction with a similar effect. Then, a removal reaction of a methyl or a benzyl
protective group as a substitute of a methoxyphenoxy group or a benzyloxy group as
a substitute is preferably performed in a way that pyridine hydrogen halide salt of
a quantity in equivalent about 2 to 20 times, or preferably about 5 to 10 times as
large as one equivalent quantity of a methyl or a benzyl protective group is used
to cause a reaction at a reflux temperature for about 1 hour or less, while with more
than a reaction time of 1 hour, a reaction product decomposes to reduce a yield. As
pyridine hydrogen halide salts, there are named pyridine hydrogen chloride salt, pyridine
hydrogen bromide salt and others. Removal of a methyl or a benzyl group as a protective
group can also be achieved using a reagent such as iodotrimethylsilane, aluminum trichloride,
aluminum tribromide, boron trifluoride, boron tribromide, hydrogen bromide, hydrogen
iodide and others.
[0031] Furthermore, in order to obtain a compound in which all of chlorine atoms of phosphonitrile
chloride are substituted with a hydroxyalkylphenoxy group (for example, a hydroxymethylphenoxy
group, a hydroxyethylphenoxy group, a hydroxybutylphenoxy group or the like), the
compound can be produced in a way that 1.01 to 2.0 equivalents of an alkali metal
salt of a hydroxyalkyl phenol is used relative to chlorine of phosphonitrile chloride
to cause a reaction preferably in an organic solvent such as benzene, toluene, xylene,
ether, tetrahydrofuran or the like at room temperature for a time ranging 1 to 20
hours, followed by the reaction at a reflux temperature of a solvent in use for a
time ranging from about 1 to about 3 hours to complete the reaction.
[0032] In order to obtain a compound in which part of chlorine atoms of phosphonitrile chlorides
substituted with a hydroxyalkylphenoxy group, a solution of an alkali metal salt of
hydroxyalkylphenol prepared so as to leave the other part of chlorine atoms of phosphonitrile
chloride unsubstituted during the reaction is added to a phosphonitrile halide solution
with a preferable result. By substituting unsubstituted chlorine atoms of partially
substituted phosphonitrile chloride with an alkali metal salt of an alcohol or phenol
compound described above, there can be obtained a compound with a hydroxyalkylphenoxy
group and R
3O-group and/or R
4O-group (R
3 and R
4 are the same as those in an aminophosphazene compound (1a) described above) as substitutes
in a mixed manner. A reaction is preferably caused in conditions of a temperature
from room temperature to a reflux temperature or lower of a solvent in use and a time
ranging about 3 to about 8 hours. Note that, in this case, a method can be adopted
in which a mixed solution of an alkali metal salt of hydroxyalkylphenol and an alkali
metal salt of alcohol or phenol compound is prepared in advance and a phosphonitrile
halide solution is dropwise added to the mixed solution to cause a reaction with a
similar effect.
[0033] As concrete examples of hydroxyphosphazene compounds (1b), there can be named, for
example, cyclotriphosphazenes with a hydroxyphenoxy group and a phenoxy group as substitutes
in a mixed manner such as hydroxyphenoxypentaphenoxycyclotriphosphazene, di(hydroxyphenoxy)-tetraphenoxycyclotriphosphazene,
tri(hydroxyphenoxy)-triphenoxycyclotriphosphazene, tetra(hydroxyphenoxy)-diphenoxycyclotriphosphazene,
penta(hydroxyphenoxy)-phenoxycyclotriphosphazene, and hexahydroxyphenoxy cyclotriphosphazene;
cyclotriphosphazenes with a hydroxymethylphenoxy group and a phenoxy group as substitutes
in a mixed manner such as hydroxymethylphenoxypentaphenoxycyclotriphosphazene, di(hydroxymethylphenoxy)-tetraphenoxycyclotriphosphazene,
tri(hydroxymethylphenoxy)-triphenoxycyclotriphosphazene, tetra(hydroxymethylphenoxy)-diphenoxycyclotriphosphazene,
penta(hydroxymethylphenoxy)-phenoxycyclotriphosphazene, and hexahydroxymethylphenoxy
cyclotriphosphazenes; cyclotriphosphazenes with a hydroxyethylphenoxy group and a
phenoxy group as substitutes in a mixed manner such as hydroxyethylphenoxy-pentaphenoxycyclotriphosphazene,
di(hydroxyethylphenoxy) -tetraphenoxycyclotriphosphazene, tri(hydroxyethylphenoxy)-triphenoxycyclotriphosphazene,
tetra(hydroxyethylphenoxy)-diphenoxycyclotriphosphazene, penta(hydroxyethylphenoxy)-phenoxycyclotriphosphazene,
and hexahydroxyethylphenoxy cyclotriphosphazenes; cyclotriphosphazenes with a hydroxybutylphenoxy
group and a phenoxy group as substitutes in a mixed manner such as hydroxybutylphenoxypentaphenoxycyclotriphosphazene,
di(hydroxybutylphenoxy)-tetraphenoxycyclotriphosphazene, tri(hydroxybutylphenoxy)-triphenoxycyclotriphosphazene,
tetra(hydroxybutylphenoxy)-diphenoxycyclotriphosphazene, penta(hydroxybutylphenoxy)-phenoxy
cyclotriphosphazene, and hexahydroxybutylphenoxy cyclotriphosphazenes.
[0034] Furthermore, there are named cyclotriphosphazenes with a hydroxyethylphenoxy group,
and a butoxy group, an octyloxy group, trifluoroethoxy group, an octafluoropentyloxy
group, an ethylphenoxy group, a naphthyloxy group, an allyloxy group, an allylphenoxy
group, a chlorophenoxy group or a trifluoromethylphenoxy group as substitutes in a
mixed manner.
[0035] Furthermore, there are named cyclotetraphosphazene, cyclopentaphosphazene, cyclohexaphosphazene,
a cyclophosphazene mixture (a mixture of cyclophosphazenes of the general formula
(1) with n being 3 to 15), a linear phosphazene mixture (a mixture of linear phosphazenes
of the general formula (1) with n = 3000 on average) and a cyclic (= cyclo) and linear
phosphazene mixture (a mixture of cyclic and linear phosphazenes of the general formula
(1) with n = 1000 on average) each with a hydroxyphenoxy group and a phenoxy group
as substitutes in a mixed manner.
[0036] Furthermore, there are named cyclotetraphosphazene, cyclopentaphosphazene, cyclohexaphosphazene,
a cyclophosphazene mixture (a mixture of cyclophosphazenes of the general formula
(1) with n being 3 to 15), a linear phosphazene mixture (a mixture of linear phosphazenes
of the general formula (1) with n = 3000 on average) and a cyclic (= cyclo) and linear
phosphazene mixture (a mixture of cyclic and linear phosphazenes of the general formula
(1) with n = 1000 on average) each with a hydroxyethylphenoxy group and a phenoxy
group as substitutes in a mixed manner. The hydroxyphosphazene compounds may include
mixtures of compounds with two or more types of substituents.
[0037] Among the above hydroxyphosphazenes, preferable are, for example, hexahydroxyphenoxycyclotriphosphazene;
hexahydroxyethylphenoxycyclotriphosphazene; a cyclotriphosphazene with a hydroxyphenoxy
group, a hydroxyethylphenoxy group and a phenoxy group as substitutes in a mixed manner;
a cyclophosphazene mixture (a mixture of cyclophosphazenes of the general formula
(1) with n being 3 to 15) with a hydroxyphenoxy group and a phenoxy group as substitutes
in a mixed manner; a linear phosphazene mixture (a mixture of linear phosphazenes
of the general formula (1) with n = 3000 on average) with a hydroxyethylphenoxy group
and a phenoxy group as substitutes in a mixed manner, and especially preferable are
a cyclophosphazene mixture (a mixture of cyclophosphazenes of the general formula
(1) with n being 3 to 15) with a hydroxyphenoxy group and a phenoxy group as substitutes
in a mixed manner and a linear phosphazene mixture (a mixture of linear phosphazenes
of the general formula (1) with n = 3000 on average) with a hydroxyethylphenoxy group
and a phenoxy group as substitutes in a mixed manner.
[Glycidylphosphazene Compound (1c)]
[0038] A glycidyl phosphazene compound (1c) can be produced in a way that a hydroxyphosphazene
compound (1b) and epihalohydrin are reacted with each other in a solvent-free condition
or in a proper solvent such as dimethyl sulfoxide in the presence of a quaternary
ammonium salt such as tetramethyl ammonium chloride, tetramethyl ammonium bromide
or the like, an alkali metal hydroxide such as sodium hydroxide, potassium hydroxide
or the like. In a case where a quaternary ammonium salt is used, since a reaction
is ceased at a stage of a ring opening addition reaction, the above reaction is followed
by addition of an alkali metal hydroxide to cause an ring closing reaction. If an
alkali metal hydroxide is added at the start of the reaction, the ring opening addition
reaction and the ring closing reaction can be performed successively.
[0039] As epihalohydrins, there can be used known compounds and the following are named:
epichlorohydrin, epibromohydrin, epiiodohydrin and others. A quantity of usage thereof
is generally in the range of from 1 to 50 mol and preferably in the range of from
3 to 15 mol per 1 mol of hydroxyl group of hydroxyphosphazene compound (1b)
[0040] In a case where dimethyl sulfoxide is used, a quantity of usage thereof has only
to be in the range of from 20 to 200 parts by weight relative to 100 parts by weight
of epihalohydrin.
[0041] A quantity of usage of an alkali metal hydroxide has only to be generally in the
range of from 0.8 to 1.5 mol and preferably in the range of from 0.9 to 1.3 mol per
1 mol of hydroxyl group of a hydroxyphosphazene compound (1b). A quantity of usage
of a quaternary ammonium salt has only to be generally in the range of 0.001 to 1
mol and preferably in the range of 0.005 to 0.5 mol per 1 mol of a hydroxyl group
of a hydroxyphosphazene compound (1b)
[0042] The reaction temperature is generally set in the range of from 20 to 130°C and preferably
in the range of from 30 to 100°C. The reaction can also be progressed while water
produced during the reaction is removed to outside the reaction system. After the
reaction ends, a salt, dimethyl sulfoxide, and others as byproducts are removed by
washing with water and epihalohydrin in excess is removed as a distillate, thereby
enabling a glycidyl phosphazene compound (1c).
[0043] In order to remove an impurity, the obtained glycidyl phosphazene compound (1c) may
be dissolved into a solvent such as methylisobutyl ketone or the like to then, cause
the solution to be heated at a temperature in the range of from 50 to 100°C for a
time in the range of from 0.5 to 3 hours in the presence of an alkali metal hydroxide
such as sodium hydroxide or the like. After the heat treatment, the solution is repeatedly
washed with water to cause a water phase to be neutral and a solvent such as methylisobutyl
ketone or the like is removed as a distillate under a reduced pressure, thereby obtaining
a glycidyl phosphazene compound (1c) with an extremely high purity. In this process,
a quantity of usage of an alkali metal hydroxide is in the range of from 0.01 to 0.2
mol per 1 mol of an epoxy group of the glycidyl phosphazene compound (1c) to be processed.
By repeating such a process, there can be obtained a glycidyl phosphazene compound
(1c) with a much higher purity.
[0044] As concrete examples of glycidyl phosphazene compounds (1b), there are named the
following compounds, for example, cyclotriphosphazenes with a glycidyloxyphenoxy group
and a phenoxy group as substitutes in a mixed manner such as glycidyloxyphenoxy-pentaphenoxycyclotriphosphazene,
di(glycidyloxyphenoxy)-tetraphenoxycyclotriphosphazene,
tri(glycidyloxyphenoxy)-triphenoxycyclotriphosphazene,
tetra(glycidyloxyphenoxy)-diphenoxycyclotriphosphazene,
penta(glycidyloxyphenoxy)-phenoxycyclotriphosphazene, and
hexaglycidyloxyphenoxy cyclotriphosphazenes; cyclotriphosphazenes with a glycidyloxymethylphenoxy
group and a phenoxy group as substitutes in a mixed manner such as glycidyloxymethylphenoxy-pentaphenoxycyclotriphosphazene,
di(glycidyloxymethylphenoxy)-tetraphenoxy cyclotriphosphazene,
tri(glycidyloxymethylphenoxy)-triphenoxycyclotriphosphazene,
tetra(glycidyloxymethylphenoxy)-diphenoxy-cyclotriphosphazene,
penta(glycidyloxymethylphenoxy)-phenoxycyclotriphosphazene, and
hexaglycidyloxymethylphenoxy cyclotriphosphazenes; cyclotriphosphazenes with a glycidyloxyethylphenoxy
group and a phenoxy group as substitutes in a mixed manner such as glycidyloxyethylphenoxy-pentaphenoxycyclotriphosphazene,
di(glycidyloxyethylphenoxy)-tetraphenoxy-cyclotriphosphazene, tri(glycidyloxyethylphenoxy)-triphenoxy
cyclotriphosphazene, tetra(glycidyloxyethylphenoxy)-diphenoxy-cyclotriphosphazene,
penta(glycidyloxyethylphenoxy)-phenoxy cyclotriphosphazene, and
hexaglycidyloxyethylphenoxycyclotriphosphazenes; cyclotriphosphazenes with a glycidyloxybutylphenoxy
group and a phenoxy group as substitutes in a mixed manner such as glycidyloxybutylphenoxy-pentaphenoxycyclotriphosphazene,
di(glycidyloxybutylphenoxy)-tetraphenoxy cyclotriphosphazene,
tri(glycidyloxybutylphenoxy)-triphenoxycyclotriphosphazene,
tetra(glycidyloxybutylphenoxy)-diphenoxy cyclotriphosphazene,
penta(glycidyloxybutylphenoxy)-phenoxy cyclotriphosphazene, and
hexaglycidyloxybutylphenoxycyclotriphosphazenes.
[0045] Furthermore, there are named cyclotriphosphazenes with a glycidyloxyethylphenoxy
group, and a butoxy group, an octyloxy group, a trifluoroethoxy group, an octafluoropentyloxy
group, an ethylphenoxy group, a naphthyloxy group, an allyloxy group, an allylphenoxy
group, a chlorophenoxy group, a trifluoromethylphenoxy group or the like as substitutes
in a mixed manner.
[0046] Furthermore, there are named cyclotetraphosphazene, cyclopentaphosphazene, cyclohexaphosphazene,
a cyclophosphazene mixture (a mixture of cyclophosphazenes of the general formula
(1) with n being 3 to 15), a linear phosphazene mixture (a mixture of linear phosphazenes
of the general formula (1) with n = 3000 on average) and a cyclic (=cyclo) and linear
phosphazene mixture (a mixture of cyclic and linear phosphazenes of the general formula
(1) with n = 1000 on average) each with a glycidyloxyphenoxy group and a phenoxy group
as substitutes in a mixed manner.
[0047] Furthermore, there are named cyclohexaphosphazene with a glycidyloxyethylphenoxy
group, a glycidyloxyethylphenoxy group, a glycidyloxyethylphenoxy group or the like,and
a phenoxy group in a mixed manner, a cyclophosphazene mixture (a mixture of cyclophosphazenes
of the general formula (1) with n being 3 to 15) with a glycidyloxyethylphenoxy group
and a phenoxy group as substitutes in a mixed manner, a linear phosphazene mixture
(a mixture of linear phosphazenes of the general formula (1) with n = 3000 on average)
with a glycidyloxyethylphenoxy group and a phenoxy group as substitutes in a mixed
manner, and a cyclic (= cyclo) and linear phosphazene mixture (a mixture of cyclic
and linear phosphazenes of the general formula (1) with n = 1000 on average) each
with a glycidyloxyethylphenoxy group and a phenoxy group as substitutes in a mixed
manner. The glycidyl phosphazene compounds may include mixtures of compounds with
two or more types of substituents.
[0048] Among the above glycidyl phosphazene compounds, preferable are, for example, hexaglycidyloxyphenoxy
cyclotriphosphazene; hexaglycidyloxyethylphenoxy cyclotriphosphazene; cyclotriphosphazene
with a glycidyloxyphenoxy group and a phenoxy group as substitutes in a mixed manner;
cyclotriphosphazene with a glycidyloxyethylphenoxy group and a phenoxy group as substitutes
in a mixed manner; a cyclophosphazene mixture (a mixture of cyclophosphazenes of the
general formula (1) with n being 3 to 15) with a glycidyloxyphenoxy group and a phenoxy
group as substitutes in a mixed manner; a linear phosphazene mixture (a mixture of
linear phosphazenes of the general formula (1) with n = 3000 on average) with a glycidyloxyethylphenoxy
group and a phenoxy group as substitutes in a mixed manner, and especially preferable
are a cyclophosphazene mixture (a mixture of cyclophosphazenes of the general formula
(1) with n being 3 to 15) with a glycidyloxyphenoxy group and a phenoxy group as substitutes
in a mixed manner and a linear phosphazene mixture (a mixture of linear phosphazenes
of the general formula (1) with n = 3000 on average) with a glycidyloxyethylphenoxy
group and a phenoxy group as substitutes in a mixed manner.
[Polymer of Phosphazene Compound (1)]
[0049] As polymers of a phosphazene compound (1), there are named, for example, polymers
obtained by polymerization of one type or two or more types of grycidylphosphazene
compounds (1c).
[Polymer of Grycidylphosphazene Compound (1c)]
[0050] A polymer of a glycidyl phosphazene compound (1c) is generally obtained by polymerizing
a glycidyl phosphazene compound (1c) while heating in a solvent-free condition or
in an organic solvent, in the presence of a catalyst such as a Lewis acid including
aluminum chloride, boron trifluoride, iron chloride and antimony chloride, an alkali
metal hydroxide including sodium hydroxide and potassium hydroxide, an organic aluminum
compound including triethyl aluminum and aluminum tributoxide and an organic zinc
compound including diethyl zinc and others or in the absence thereof. In a case where
hexaglycidyloxyphenoxy cyclotriphosphazene is used, for example, a reaction is caused
in an organic solvent such as benzene, toluene, xylene, ether or tetrahydrofuran in
the presence of potassium hydroxide as a catalyst at a temperature in the range of
from 50°C to a reflux temperature of a solvent in use for a time in the range of from
1 to 20 hours and thereafter, the solvent and the catalyst used in the reaction are
removed through operations such as concentration, washing and others, thereby obtaining
the target compound.
[0051] As concrete examples of polymers of a glycidyl phosphazene compound (1c), there are
named the following polymers, for example, oligo or poly(glycidyloxyphenoxy-pentaphenoxy
cyclotriphosphazene), oligo or poly(tri(glycidyloxyphenoxy)-triphenoxycyclotriphosphazene),
oligo or poly(hexaglycidyloxyphenoxy-cyclotriphosphazene); oligo or poly(glycidyloxyethylphenoxy-pentaphenoxy
cyclotriphosphazene), oligo or poly(tri(glycidyloxyethylphenoxy)-triphenoxy cyclotriphosphazene),
oligo or poly(hexaglycidyloxyethylphenoxycyclotriphosphazene), a polymer of a cyclophosphazene
mixture (a mixture of cyclophosphazenes of the general formula (1) with n being 3
to 15) with a glycidyloxyphenoxy group and a phenoxy group as substitutes in a mixed
manner, a polymer of a cyclophosphazene mixture (a mixture of cyclophosphazenes of
the general formula (1) with n being 3 to 15) with a glycidyloxyethylphenoxy group
and a phenoxy group as substitutes in a mixed manner, a polymer of a cyclic (= cyclo)
and linear phosphazene mixture (a mixture of cyclic and linear phosphazenes of the
general formula (1) with n being 1000 on average) with a glycidyloxyphenoxy group
and a phenoxy group as substitutes in a mixed mannerand, and a polymer of a cyclic
(= cyclo) and linear phosphazene mixture (a mixture of cyclic and linear phosphazenes
of the general formula (1) with n being 1000 on average) with a glycidyloxyethylphenoxy
group and a phenoxy group. as substitutes in a mixed manner.
[0052] Among the polymers, preferable are oligo or poly(glycidyloxyphenoxy-pentaphenoxycyclotriphosphazene),
oligo or poly(glycidyloxyethylphenoxypentaphenoxy-cyclotriphosphazene), a polymer
of a cyclophosphazene mixture (a mixture of cyclophosphazenes of the general formula
(1) with n being 3 to 15) with a glycidyloxyphenoxy group and a phenoxy group as substitutes
in a mixed manner, a polymer of a cyclophosphazene mixture (a mixture of cyclophosphazenes
of the general formula (1) with n being 3 to 15) with a glycidyloxyethylphenoxy group
and a phenoxy group as substitutes in a mixed manner, and especially preferable are
a polymer of a cyclophosphazene mixture (a mixture of cyclophosphazenes of the general
formula (1) with n being 3 to 15) with a glycidyloxyphenoxy group and a phenoxy group
as substitutes in a mixed manner, a polymer of a cyclophosphazene mixture (a mixture
of cyclophosphazenes of the general formula (1) with n being 3 to 15) with a glycidyloxyethylphenoxy
group and a phenoxy group as substitutes in a mixed manner and others.
[Reaction Compound between Phosphazene Compound (1) and Other Compounds]
[0053] As reaction compounds of a phosphazene compound (1) with at least one type of compound
selected from the group consisting of an epoxy compound, a phenol compound, an amine
compound and an acid anhydride (the compounds are hereinafter referred collectively
to as a reactive group containing compound unless otherwise specified), there are
named the following copolymers, for example, a copolymer obtained by polymerizing
an aminophosphazene compound (1a) and/or a hydroxyphosphazene compound (1b) with an
epoxy compound, a copolymer obtained by polymerizing a glycidylphosphazene compound
(1c) with a reactive group containing compound and others.
[Copolymer of Aminophophazene Compound (1a) and/or Hydroxyphosphazene Compound (1b)
with Epoxy Compound]
[0054] Copolymerization of an aminophosphazene compound (1a) and/or a hydroxyphosphazene
compound (1b) with an epoxy compound is performed, for example, by heating in an organic
solvent or in a solvent-free condition in the presence or absence of a curing catalyst.
In a case where hexaaminophenoxy cyclotriphosphazene or hexahydroxyphenoxy cyclotriphosphazene
reacts with diglycidyl ether of bisphenol A, for example, a reaction has only to be
caused in an organic solvent such as benzene, toluene, xylene, ether, tetrahydrofuran
or the like using potassium hydroxide as a curing catalyst at a temperature in the
range of from 50°C to a reflux temperature of a used solvent for a time in the range
of from 1 to 20 hours and after the reaction ends, the solvent and the used catalyst
are removed by operations such as concentration, washing and others, thereby enabling
a desired copolymer to be obtained.
[0055] As epoxy compounds, there can be used an epoxy resin and a monomer for an epoxy resin.
Epoxy resins can be the same as the known epoxy resins described above. Known monomers
can be used as a monomer for epoxy resin and there can be named, for example, bifunctional
epoxy compounds such as ethylene glycol diglycidyl ether, propylene glycol diglycidyl
ether, tripropylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, diglycidyl
ether of bisphenol A, butadiene diepoxide, 3,4-epoxycyclohexylmethyl-(3,4-epoxy)cyclohexane
carboxylate, vinylcyclohexane dioxide, 4,4',-di(1,2-epoxyethyl)diphenyl ether, 4,4'-(1,2-epoxyethyl)biphenyl,
2,2-bis(3,4-epoxycyclohexyl)propane, glycidyl ether of resorcinol, diglycidyl ether
of phloroglucin, diglycidyl ether of methyl phloroglucin, bis(2,3-epoxycyclopentyl)
ether, 2-(3,4-epoxy)cyclohexane-5,5-spiro(3,4-epoxy)cyclohexane-m-dioxane, bis(3,4-epoxy-6-methylcyclohexyl)adipate,
N,N'-m-phenylenebis(4,5-epoxy-1,2-cyclohexane)dicarboxyimide; tri- or higher functional
epoxy compounds such triglycidyl ether of p-aminophenol, polyallyl glycidyl ether,
1,3,5-tri(1,2-epoxyethyl)benzene, 2,2',4,4'-tetraglycidoxybenzophenone, polyglycidyl
ether of phenol formaldehyde novolak, triglycidyl ether of trimethylolpropane and
others. Epoxy resins and monomers thereof are used singly or in a combination of two
or more thereof.
[0056] As concrete examples of copolymers between an aminophosphazene compounds (1a) and
an epoxy compound, there are named the following copolymers, for example, between
epoxy compounds such as diglycidyl ether of bisphenol A, 4,4'-(1,2-epoxyethyl)biphenyl,
2,2-bis(3,4-epoxycyclohexyl)propane, glycidyl ether of resorcinol, diglycidyl ether
of fluoroglucin or the like; and hexaaminophenoxy cyclotriphosphazene, hexaaminoethylphenoxy
cyclotriphosphazene, a cyclotriphospazene with an aminophenoxy group and a phenoxy
group as substitutes in a mixed manner, a cyclotriphospazene with an aminoethylphenoxy
group and a phenoxy group as substitutes in a mixed manner, a cyclophosphazene mixture
(a mixture of cyclophosphazenes of the general formula (1) with n being 3 to 15) with
an aminophenoxy group and a phenoxy group as substitutes in a mixed manner, a linear
phosphazene mixture (a mixture of linear phosphazenes of the general formula (1) with
n = 3000 on average) with an aminoethylphenoxy group and a phenoxy group as substitutes
in a mixed manner or the like. The copolymers can be used singly or in a combination
of two or more thereof. In a reaction between an aminophosphazene compound (1a) and
an epoxy compound, a terminal end of a copolymer produced from the reaction may be
an amino group or an epoxy group according to a quantitative relation therebetween.
[0057] As concrete examples of copolymers between a hydroxyphosphazene compounds (1b) and
an epoxy compound, there are named the following copolymers, for example, between
hexahydroxyphenoxy cyclotriphosphazene, hexahydroxyethylphenoxy cyclotriphosphazene,
a cyclotriphospazene with a hydroxyphenoxy group and a phenoxy group as substitutes
in a mixed manner, a cyclotriphosphazene with a hydroxyethylphenoxy group and a phenoxy
group as substitutes in a mixed manner, a cyclophosphazene mixture (a mixture of cyclophosphazenes
of the general formula (1) with n being 3 to 15) with a hydroxyphenoxy group and a
phenoxy group as substitutes in a mixed manner, a linear phosphazene mixture (a mixture
of linear phosphazenes of the general formula (1) with n being 3000 on average) with
a hydroxyphenoxy group and a phenoxy group as substitutes in a mixed manner or the
like; and diglycidyl ether of bisphenol A, 4,4'-(1,2-epoxyethyl)biphenyl, 2,2-bis(3,4-epoxycyclohexyl)propane,
glycidyl ether of resorcinol, diglycidyl ether of phloroglucin or the like. The copolymers
can be used singly or in a combination of two or more thereof. In a reaction between
a cyclic hydroxyphosphazene compound (1b) and an epoxy compound, a terminal end of
a copolymer produced from the reaction may be a hydroxy group or an epoxy group according
to a quantitative relation therebetween.
[Copolymer of Glycidylphophazene Compound (1c)) with Reactive Group Containing Compound]
[0058] A copolymer between a glycidylphosphazene compound (1c) and a reactive group containing
compound can be produced by a reaction of a glycidylphosphazene compound (1c) with
a reactive group containing compound.
[0059] As epoxy compounds, there can be used epoxy compounds similar to those used in a
case of production of a copolymer between an aminophosphazene compound (1a) and/or
a hydroxyphosphazene compound (1b) and an epoxy compound. Herein as well, epoxy compounds
can be used singly or in a combination of two or more thereof. As concrete examples
of copolymers between a glycidylphosphazene compounds (1c) and an epoxy compound,
there are named the following copolymers, for example, between diglycidyl ether of
bisphenol A, or glycidyl ether of 4,4'-(1,2-epoxyethyl)biphenyl, 2,2-bis(3,4-epoxycyclohexyl)propane
or resorcinol, or diglycidyl ether of phloroglucin or the like; and hexaglycidylphenoxy
cyclotriphosphazene, hexaglycidylethylphenoxy cyclotriphosphazene, a cyclotriphosphazene
with a glycidyloxyphenoxy group and a phenoxy group as substitutes in a mixed manner,
a cyclotriphosphazene with a glycidyloxyethylphenoxy group and a phenoxy group as
substitutes in a mixed manner, a cyclophosphazene mixture (a mixture of cyclophosphazenes
of the general formula (1) with n being 3 to 15) with a glycidyloxyphenoxy group and
a phenoxy group as substitutes in a mixed manner, a linear phosphazene mixture (a
mixture of linear phosphazenes of the general formula (1) with n = 3000 on average)
with a glycidyloxyphenoxy group and a phenoxy group as substitutes in a mixed manner
or the like. In the copolymers, a terminal end of each polymer may be a phosphazene
compound or an epoxy compound. These copolymers can be used singly or in a combination
of two or more thereof.
[0060] As concrete examples of copolymers between a glycidylphosphazene compound (1c) and
a phenol compound, there are named the following copolymers, for example, between
resins obtained by condensation of bisphenol A, bisphenol F, dihydroxynaphthalene,
phenol, cresol or xylenol and formaldehyde in the presence of an acidic catalyst,
p-vinyl phenol resin, triphenolmethane condensate or the like; and hexaglycidylphenoxy
cyclotriphosphazene, hexaglycidylethylphenoxy cyclotriphosphazene, a cyclotriphospazene
with a glycidyloxyphenoxy group and a phenoxy group as substitutes in a mixed manner,
a cyclotriphospazene with a glycidyloxyethylphenoxy group and a phenoxy group as substitutes
in a mixed manner, a cyclophosphazene mixture (a mixture of cyclophosphazenes of the
general formula (1) with n being 3 to 15) with a glycidyloxyphenoxy group and a phenoxy
group as substitutes in a mixed manner, a linear phosphazene mixture (a mixture of
linear phosphazenes of the general formula (1) with n being 3000 on average) with
a glycidyloxyphenoxy group and a phenoxy group as substitutes in a mixed manner or
the like. In the copolymers, a terminal end of each polymer may be a glycidyl group
or a hydroxy group. The copolymers can be used singly or in a combination of two or
more thereof.
[0061] As amine compounds, there may be named the following compounds such as diethylenetriamine,
triethylenetetramine, tetraethylenepentamine, diethylaminopropylamine, polyamidepolyamine,
menthenediamine, isophrone diamine, N-aminoethylpiperazine, bis(4-amino-3-methylcyclohexyl)methane,
bis(4-aminocyclohexyl)methane, m-xylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone,
m-phenylenediamine, dicyandiamide, adipic acid dihydrazide, 3,9-bis(3-aminoporpyl)-2,4,8,10-tetraoxaspiro(5,5)undecane
adduct and others. The amine compounds can be used singly or in a combination of two
or more thereof.
[0062] As concrete examples of copolymers between a glycidylphosphazene compound (1c) and
an amine compound, there are named the following copolymers, for example, between
an amine compound such as tetraethylenepentamine, m-xylenediamine, diaminodiphenylmethane,
diaminodiphenylsulfone, m-phenylenediamine, dicyandiamide or the like; and hexaglycidylphenoxy
cyclotriphosphazene, hexaglycidylethylphenoxy cyclotriphosphazene, a cyclotriphospazene
with a glycidylphenoxy group and a phenoxy group as substitutes in a mixed manner,
a cyclotriphospazene with a glycidylethylphenoxy group and a phenoxy group as substitutes
in a mixed manner, a cyclophosphazene mixture (a mixture of cyclophosphazenes of the
general formula (1) with n being 3 to 15) with a glycidylphenoxy group and a phenoxy
group as substitutes in a mixed manner, a linear phosphazene mixture (a mixture of
linear phosphazenes of the general formula (1) with n = 3000 on average) with a glycidylphenoxy
group and a phenoxy group as substitutes in a mixed manner or the like. In the copolymers,
a terminal end of each polymer may be a glycidyl group or an amino group. The copolymers
can be used singly or in a combination of two or more thereof.
[0063] As acid anhydrides, there are named the following anhydrides, for example, phthalic
anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic
anhydride, methylhexahydrophthalic anhydride, methylnadic anhydride, dodecylsuccinic
anhydride, chlorendic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic
anhydride, ethyleneglycol bis(anhydrotrimate), methylcyclohexanetetracarboxylic anhydride,
trimellitic anhydride, polyazelaic anhydride and others. The anhydrides can be used
singly or in a combination of two or more thereof. As concrete examples of copolymers
between a glycidylphosphazene compound (1c) and an acid anhydride, there are named
the following copolymers, for example, between tetrahydrophthalic anhydride, hexahydrophthalic
anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride,
pyromellitic anhydride, benzophenonetetracarboxylic anhydride, methylcyclohexanetetracarboxylic
anhydride or the like; and hexaglycidylphenoxy cyclotriphosphazene, hexaglycidylethylphenoxy
cyclotriphosphazene, a cyclotriphosphazene with a glycidyloxyphenoxy group and a phenoxy
group as substitutes in a mixed manner, a cyclotriphosphazene with a glycidyloxyethylphenoxy
group and a phenoxy group as substitutes in a mixed manner, a cyclophosphazene mixture
(a mixture of cyclophosphazenes of the general formula (1) with n being 3 to 15) with
a glycidyloxyphenoxy group and a phenoxy group as substitutes in a mixed manner, a
linear phosphazene mixture (a mixture of linear phosphazenes of the general formula
(1) with n = 3000 on average) with a glycidyloxyphenoxy group and a phenoxy group
as substitutes in a mixed manner or the like. In the copolymers, a terminal end of
each polymer may be a glycidyl group or an acid residue. The copolymers can be used
singly or in a combination of two or more thereof.
(C) Component: epoxy hardener
[0064] As epoxy hardeners, there are named a compound having a phenolic hydroxyl group,
an aromatic amine compound, an acid anhydride and others. Among them, preferable is
a compound having a phenolic hydroxyl group in consideration of moisture resistance,
moldability, storage stability and others. As compounds each having a phenolic hydroxyl
group, there are named, without a specific limitation imposed on compounds as far
as the compounds show a curing action exerted to an epoxy resin, for example, resins
obtained by condensation or co-condensation of a phenol such as phenol, cresol, xylenol,
resorcinol, catechol, bisphenol A or bisphenol F, or a naphthol such as α-naphthol,
β-naphthol or dihydroxynaphthalene with an aldehyde such as formaldehyde, acetaldehyde,
propionaldehyde, benzaldehyde or salicylaldehyde in the presence of an acidic catalyst,
p-vinyl phenol resin, phenol-aralkyl resin having a xylylene group, synthesized from
a phenol and dimethoxy-p-xylene, dicyclopentadiene-modified phenol resin, triphenolmethane
condensate and others. These can be used singly or in a combination of two or more
thereof.
(D) Components: Inorganic Filler
[0065] An inorganic filler has a characteristic not only to enhance a dripping preventive
effect of a resin composition but to also improve a mechanical strength thereof. As
inorganic filler, while any of inorganic filler commonly used in this field can be
employed, there can be named the following: for example, powder of fused silica, crystal
silica, alumina, aluminum hydroxide, magnesium hydroxide, zinc oxide, zinc borate,
zircon, antimony trioxide, talc, calcium silicate, calcium carbonate, silicon carbide,
boron carbide, beryllia, zirconia, titanium white, clay, mica, talc and others; beads
produced from the above powder; kaolin, barium sulfate, barium carbonate, calcium
sulfate, titanium oxide, glass beads, glass balloons, glass flakes, fibrous alkali
metal titanate (sodium titanate fibers and others), fibrous borate (aluminum borate
fibers, magnesium borate fibers and others), zinc oxide fibers, titanium oxide fibers,
magnesium oxide fibers, gypsum fibers, aluminum silicate fibers, calcium silicate
fibers, silicon carbide fibers, titanium carbide fibers, titanium nitride fibers,
carbon fibers, alumina-silica fibers, zirconia fibers, quartz fibers, thin titanate
flakes, thin titanium dioxide flakes and others. The inorganic filler can be used
singly or in a combination of two or more thereof.
[Compounding Proportions of Components]
[0066] Compounding proportions of components (A) to (D) described above in a composition
of the present invention meet the following relation, in which, as to components of
an epoxy resin (A), a phosphazene compound (B), an epoxy hardener (C) and an inorganic
filler (D), the component (B) has only to be in the range of from 0.01 to 70 % by
weight and preferably in the range of from 0.1 to 60 % by weight and the component
(C) has only to be up to 70 % by weight and preferably up to 60 % by weight relative
to a total quantity of the components (A) to (C), and the component (D) has only to
be up to 95 % by weight and preferably up to 90 % by weight relative to a total quantity
of the components (A) to (D).
[0067] A type of epoxy resin and types of other components used together have only to be
selected within the ranges of compounding quantities described above giving consideration
to performance required of a target flame-retardant epoxy resin composition, a type
of a laminate manufactured using the flame-retardant epoxy resin composition, types
of an encapsulating material and a material of a casting mold, and an effect of further
improving performance of flame retardance, moisture resistance, soldering heat resistance,
mechanical properties and moldability of a flame-retardant epoxy resin composition
to be obtained.
[0068] While no specific limitation is placed on an equivalent ratio of an epoxy resin (A)
and a functional group of a component (C) (the number of groups of (C)/the number
of epoxy groups of (A)), the ratio is preferably set in the range of from 0.7 to 1.3
in order to suppress respective unreacted portions low.
[0069] Since a phosphazene compound as a (B) component works not only as a flame retardant
but also as an epoxy resin or an epoxy hardener, an equivalent ratio of an epoxy resin
as a component (A), a phosphazene compound as a component (B) and a functional group
of an epoxy hardener as a component (C) are preferably all set in the range of from
0.7 to 1.3.
[0070] Preferred embodiments of a flame-retardant epoxy resin composition of the present
invention will be shown below.
- (1) A flame-retardant epoxy resin composition in which as to components of an epoxy
resin (A) and a phosphazene compound (B), the phosphazene compound component (B) is
compounded in the range of from 0.01 to 70 % by weight (and preferably in the range
of from 0.1 to 60 % by weight) relative to a total quantity of the components (A)
and (B).
- (2) A flame-retardant epoxy resin composition in which as to components of an epoxy
resin (A), a phosphazene compound (B) and an epoxy hardener (C), the phosphazene compound
component (B) is compounded in the range of from 0.01 to 70 % by weight (and preferably
in the range of from 0.1 to 60 % by weight) and the epoxy hardener component (C) is
compounded up to 70% by weight (and preferably up to 60 % by weight) relative to a
total quantity of the components (A), (B) and (C).
- (3) A flame-retardant epoxy resin composition in which as to components of an epoxy
resin (A), a phosphazene compound (B), an epoxy hardener (C) and an inorganic filler
(D), the phosphazene compound component (B) is compounded in the range of from 0.01
to 70 % by weight (and preferably in the range of from 0.1 to 60 % by weight), the
epoxy hardener component (C) is compounded up to 70 % by weight (and preferable up
to 60 % by weight) relative to a total quantity of the components (A), (B) and (C);
and the inorganic filler component (D) is compounded up to 95 % by weight (and preferably
up to 90 % by weight) relative to a total quantity of the components (A), (B). (C)
and (D).
- (4) A flame-retardant epoxy resin composition in which a polymer of a cyclic and/or
a chain phosphazene compound of the general formula (1) is compounded as a phosphazene
compound (B) in any one of the flame-retardant epoxy resin compositions (1), (2) and
(3)
- (5) A flame-retardant epoxy resin composition obtained by compounding any one of the
flame-retardant epoxy resin compositions (1), (2), (3) and (4) into a thermoplastic
resin and/or a thermoset resin.
[Other Components]
[0071] A curing accelerator may be included in a flame-retardant epoxy resin composition
of the present invention in addition to the above components. As curing accelerators,
there can be used accelerators known in this field and there can be named the following,
for example, basic active hydrogen compounds such as dicyandiamide and adipic acid
hydrazide; bicycloamidines such as 1,8-diazabicyclo(5,4,0)undecene-7 and 1,5-diazabycyclo(3,4,0)nonene-5,
and derivatives such as phenolates thereof, octyl salts thereof and oleic acid salts
thereof; oxyalkylamines such as triethanolamine, tetramethylbutanediamine, tetramethylpentanediamine,
tetramethylhexanediamine, triethylenediamine, dimethylaniline, benzyl dimethylamine,
dimethylaminoethanol and dimethylaminopentanol; tertiary amines such as tris(dimethylaminomethyl)phenol,
N-methylmorpholine and N-ethylmorpholine; imidazoles such as 2-methylimidazole, 2-ethylimidazole,
2-phenylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-methyl-4-ethylimidazole,
2-phenyl-4-methylimidazole, 1-butylimidazole, 1-propyl-2-methylimidazole, 1-bezyl-2-methylimidazole,
1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-phenylimidazole,
1-azine-2-methylimidazole and 1-azine-2-uindecylimidazole; quaternary ammonium salts
such as cetyl trimethyl ammonium bromide, cetyl trimethyl ammonium chloride, dodecyl
trimethyl ammonium iodide, trimethyl decyl ammonium chloride, benzyl dimethyl tetradecyl
ammonium chloride, benzyl methyl palmityl ammonium chloride, allyl dodecyl trimethyl
ammonium bromide and benzyl dimethyl tetradecyl ammonium acetate; organic phosphines
such as tributyl phosphine, methyl diphenyl phosphine and triphenyl phosphine; and
tetraphenyl borates such as triphenylphosphine tetraphenyl borate, tetraphenylphosphonium
tetraphenyl borate, triethylamine tetraphenyl borate, N-methylmorpholine tetraphenyl
borate, 2-ethyl-4-methylimidazole tetraphenyl borate and 2-ethyl-1,4-dimethylimidazole
tetraphenyl borate. The curing accelerators can be used singly or in a combination
of two or more thereof.
[0072] Fluororesin and others can be compounded into a flame-retardant epoxy resin composition
of the present invention for the purpose to improve flame-retardant performance, especially
dripping (fire spreading due to dripping in burning) preventive performance to a higher
level. As fluororesin, there can be used known fluororesin which are named, for example,
polytetrafluoroethylene (PTFE), tetrafluoroethylene-hexafluoropropylene copolymer
(FEP), tetrafluoroethylene-perfluoroalkylvinylether copolymer (PFA), tetrafluoroethylene-ethylene
copolymer (ETFE), poly(trifluorochloroethylene) (CTFE), polyfluorovinylidene (PVdF)
and others. Among them, preferable is PTFE. Fluororesins can be used singly or in
a combination of two or more thereof. No specific limitation is placed on a compounding
quantity of fluororesin and in a case of a composition of the present invention consisting
of an epoxy resin (A), a phosphazene compound (B) and an epoxy hardener (C), a compounding
quantity of fluororesin is generally on the order in the range of from 0.01 to 2.5
% by weight and preferably on the order in the range of from 0.1 to 1.2 % by weight
relative to a total quantity of the epoxy resin (A), the phosphazene compound (B)
and the epoxy hardener (C), though a compounding quantity thereof can be properly
selected in a wide range according to various conditions such as a type of an epoxy
resin, a quantity of usage of a flame retardant, types and compounding quantities
of other additive agents, an application for a flame-retardant resin composition to
be obtained.
[0073] Various types of additive agents can be compounded into a flame-retardant epoxy resin
composition of the present invention in a range in which preferable characteristics
thereof are not lost at any degree. As the additive agents, there are named, for example,
the curing accelerator, natural waxes, synthetic waxes, straight-chain aliphatic acids
and salts thereof, acid amides, esters, release agents such as paraffins, phosphazene
compounds other than phosphazene compounds as the components (B) of the present invention,
phosphate esters, condensed phosphate esters, other organic phosphorus compounds;
flame retardants such as phosphorus as an element, red phosphorus, chlorinated paraffin,
brominated toluene, hexabromobenzene, antimony trioxide and other inorganic flame
retardants; colorants such as carbon black and red iron oxide; and coupling agents
(silane coupling agents such as 3-glycidoxypropyltrimethoxy silane and titanium based
coupling agents such as tetraoctylbis(phosphite)titanate and others). The additives
can be used singly or in a combination of two or more thereof.
[0074] General resin additive agents can further be compounded into a flame-retardant epoxy
resin composition of the present invention in a range in which preferable characteristics
thereof are not lost at any degree. While no specific limitation is imposed thereon,
there are named, for example, ultraviolet absorbents such as benzophenone based, benzotriazole
based, cyanoacrylate based, triazine based and others, a light stabilizing agent such
as hindered amine based, antioxidants such as hindered phenol, organic phosphorus
based peroxide decomposing agent, organic sulfur based peroxide decomposing agent;
light intercepting agents such as rutile type titanium oxide, zinc oxide, chromium
oxide, cerium oxide and others; metal deactivating agents such as benzotriazole based
and others; quenching agents such as organic nickel compound and others; an anti-cloudness
agent, an anti-mold agent, an antibacterial agent, pigments and others.
[0075] A flame-retardant epoxy resin composition of the present invention can be produced
by mixing and/or kneading prescribed quantities or proper quantities of an epoxy resin
(A), a phosphazene compound (B), an epoxy hardener (C), an inorganic filler (D) and,
when required, furthermore, fluororesin and other flame retardants according to a
known method. Mixing of the components have only to be performed in a proper sequence
of operations, and two or more types among mixed component composites and single components
may be mixed to one compound prior to the usage.
[0076] As flame retardants for other synthetic resins, there may be used one type or two
or more types of polymers selected from the group consisting of the phosphazene compounds
(1) and one type or two or more types selected from the group consisting of reaction
products obtained from a reaction of a phosphazene compound (1) with a reactive group
containing compound. As the synthetic resins, no specific limitation is placed thereon
but there can be used any one of known thermoplastic resin and/or thermoset resin.
As concrete examples of thermoplastic resins, there are named the following resins:
polyethylene, polypropylene, polyisoprene, chlorinated polyethylene, polyvinyl chloride,
polybutadiene, polystyrene, high-impact polystyrene, acrylonitrile-styrene resin (AS
resin), acrylonitrile-butadiene-styrene resin (ABS resin), methyl methacrylate-butadiene-styrene
resin (MBS resin), methyl methacrylate-acrylonitrile-butadiene-styrene resin (MABS
resin), acrylonitrile-acrylic rubber-styrene resin (AAS resin), poly(methyl (meta)acrylate),
polyester (polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate
and others), polycarbonate, polyphenylene ether (PPE), modified polyphenylene ether,
polyamide (aliphatic and/or aromatic), polyphenylene sulfide, polyimide, poly(ether
ether ketone), polysulfone, polyallylate, poly(ether ketone) poly(ether nitrile),
poly(thioether sulfone), poly(ether sulfone), polybenzimidazole, polycarbodiimide,
polyamidimide, poly(etherimide), a liquid crystal polymer and others. Among them,
preferable are polyester, ABS resin, polycarbonate, modified polyphenylene ether,
polyamide and others. As concrete examples of thermoset resins, there are named the
following resins: for example, polyurethane, phenol resin, melamine resin, bismaleimide-triazine
resin, urea resin, unsaturated polyester resin, diallyl phthalate resin, silicone
resin, epoxy resin (bisphenol-A epoxy resin, bisphenol-F epoxy resin, bisphenol-AD
epoxy resin, phenol novolak epoxy resin, cresol novolak epoxy resin, cycloaliphatic
epoxy resin, glycidyl ester based epoxy resin, glycidyl amine based epoxy resin, heterocyclic
epoxy resin, urethane-modified epoxy resin, brominated bisphenol-A epoxy resin and
others) and others. Among them, preferable are polyurethane, phenol resin, melamine
resin, epoxy resin and others and especially preferable is epoxy resin. The thermoplastic
resins and the thermoset resins each are employed singly or in a combination of two
or more thereof. No specific limitation is placed on a compounding quantity of a flame
retardant into a synthetic resin, but the flame retardant quantity thereof is generally
on the order in the range of from 0.01 to 100 parts by weight and preferably on the
order in the range of from 0.5 to 60 parts by weight relative to 100 parts by weight
of a synthetic resin, though a compounding quantity thereof can be properly selected
in a wide range according to various conditions such as types of a synthetic resin
and a flame retardant, a type and a compounding quantity of another additive agent,
required performance, an application and others of a resin composition to be obtained.
In the resin composition, there can be compounded one type or two or more types of
additive agents selected from the group consisting of the components shown in the
section of [Inorganic filler] and the various additives shown in the section of [Other
components]. The resin composition can be produced by mixing and/or kneading a synthetic
resin, a flame retardant and when required, other additive agents. Furthermore, molded
articles of various shapes can be formed using common molding means for synthetic
resin.
[0077] Moreover, a flame-retardant epoxy resin composition of the present invention may
be compounded into one of the various types of synthetic resin described above to
produce a new flame-retardant resin composition.
[0078] In a case where a flame-retardant epoxy resin composition of the present invention
is compounded into a thermoplastic and/or a thermoset resin, a mixture composed of
various types of components in the form of powder, beads, flakes or pellets has only
to be mixed and/kneaded into a compound using an extruder such as a single screw extruder,
a double screw extruder or the like, a Banbury mixer, a pressure kneader, or a kneader
with a twin-roll type or the like. Then, a molded article of any shape can be produced
according to a known molding method such as press molding, injection molding, extrusion
molding, casting or the like.
[Applications]
[0079] An flame-retardant epoxy resin composition of the present invention thus obtained
can be applied to various types of fields where a synthetic resin can be used and
used especially as electronic part materials such as laminate material, encapsulating
material, optical material, casting material and others in fields of electrical, electronic
and communication equipment, and precision equipment. Furthermore, a flame-retardant
epoxy resin composition of the present invention can be applied in common ways of
usage of an epoxy resin such as paint, adhesive agent, a transportation vehicle and
equipment, fiber products, various types of fabrication machines, food packaging films
and a vessel, articles associated with agriculture, forest and fishery, materials
for civil engineering and building, medical supplies, components of furniture; composite
material for aerospace use and others.
[0080] More detailed description will be given for applications as electronic parts in fields
of electrical, electronic and communication equipment, and precision equipment.
(1) Prepreg and Copper Clad Laminate
[0081] A flame-retardant epoxy resin composition of the present invention is used in paper
base copper clad laminate, a glass cloth base copper clad laminate, composite copper
clad laminate, a flexible copper clad laminate and others to construct an electronic
part. A laminate can be fabricated using a known method. For example, a process goes
this way: a proper sheet-like substrate such as glass cloth is impregnated with a
varnish including a flame-retardant epoxy resin composition of the present invention
to form a prepreg and thereafter, prepregs are used to fabricate a copper clad laminate
or the like.
[0082] As sheet like substrates for use in preparation of prepreg, substrates that are commonly
used in this field can be used, which are named, for example,: glass woven cloth,
glass non-woven cloth and cloth composed of components other than a glass such as
paper or aramid fibers.
[0083] A varnish used for fabricating a prepreg can be prepared by dissolving an epoxy resin
composition of the present invention into an organic solvent. As organic solvents,
no specific limitation is imposed thereon as far as an epoxy resin composition of
the present invention can be dissolved thereinto, which are named, for example, toluene,
xylene, acetone, methylethyl ketone, methylisobutyl ketone, N,N,-dimethylformamide,
N-methylpyrrolidone, dimethyl sulfoxide, trichloroethylene, trichloroethane, methylene
chloride, dioxane, ethyl acetate and others. Furthermore, various types of coupling
agents may be added into a varnish in order to improve a close adherence ability on
a sheet-like substrate.
[0084] One to several prepregs obtained are placed between two copper foils and the prepregs
with the two copper foils are hot pressed at a temperature of the order between 100
to 250°C under pressure between 0.1 to 10 MPa to mold, thereby fabricating a double
sided copper clad substrate for conductive circuit formation. After a circuit pattern
is formed on the double sided substrate, a necessary number of double sided copper
clad substrates are placed between the prepreg sheets, and the substrates and the
sheets are hot pressed at a temperature of the order between 100 to 250°C under a
pressure between 0.1 to 10 MPa for adhesion-molding to obtain a multilayer board.
After the adhesion-molding, holes for interlayer conduction are formed in the multilayer
board, the holes are copper plated to achieve interlayer conduction and a conductor
of the outermost layer is formed, thereby enabling a copper laminate to be obtained.
(2) Build-up Type Multilayer Printed Wiring Board
[0085] A flame-retardant epoxy resin composition of the present invention is used as materials
of a build-up type multilayer printed wiring board, for example, materials of an interlayer
insulating film, a solder resist, a resin coated copper foil and others to construct
an electronic part.
[0086] To be concrete, a flame-retardant epoxy resin composition of the present invention
and other components when required are at first dissolved into a proper organic solvent
such as toluene, methylethyl ketone, methylcellosolve or the like to prepare a varnish,
the varnish is applied on a copper foil or a carrier film such as made of polyester
or polyimide to dry the varnish coat by heating and to thereby semi-harden the coat,
which is a common method, thus fabricating a carrier-provided resin film. Then, carrier-provided
resin films are, according to a common method, laminated on an inner layer circuit
sheet (a glass epoxy laminate) serving as a core by heating under pressure with a
laminator, one of various types, to obtain a build-up type multilayer printed wiring
board.
[0087] In a case where a component to be cured by energy rays such as ultraviolet rays or
electron rays is contained in a flame-retardant epoxy resin composition of the present
invention, the composition can be used as solder resist material (solder resist ink)
capable of developing and printing.
(3) Adhesive agent and Flexible printed wiring board
[0088] By applying a flame-retardant epoxy resin composition of the present invention on
a heat resistant resin film or a conductive foil as an adhesive agent for a electronic
part, there can be obtained a flexible printed wiring board such as a single sided
flexible printed wiring board, a double sided flexible printed wiring board, a multilayer
flexible printed wiring board and others. As heat resistant resin films, while no
specific limitation is placed thereon as far as the films are self-extinguishing and
contain no halogen, there are named polyimide film, polyethyleneterephthalate film,
polyethylenenaphthalate film and others among which a polyimide film is especially
preferable from the viewpoint of heat resistance, mechanical properties, electrical
characteristics, a flame retardance and others. As conductive foils, there are named
a copper foil, an aluminum foil, a nickel foil, a stainless foil, alloy foils such
as an iron-nickel foil and others, among which a copper foil is especially preferable
in an aspect of flexibility, electrical characteristics, machinability and others.
(4) Anisotropic Conductivity Material
[0089] A flame-retardant epoxy resin composition of the present invention is used in an
adhesive agent with anisotropic conductivity, a sheet with anisotropic conductivity,
a film with anisotropic conductivity, a paste material with anisotropic conductivity
and the like for use in electrical connection of a finely patterned circuit of a liquid
crystal display (LCD) and a tape carrier package (TCP), TCP and a printed circuit
substrate (PCB) and others, thus constructing an electronic part.
(5) Semiconductor Encapsulating Material and Opto-device Encapsulating Material
[0090] A flame-retardant epoxy resin composition of the present invention is used in a semiconductor
encapsulating material and an opto-device encapsulating material, for example film
semiconductor encapsulating material, high thermal conductivity semiconductor encapsulating
material, area bump package encapsulating material, bump bonding structure encapsulating
material, flip chip encapsulating material, lead-free solder encapsulating material,
flip chip mounting under-fill material, wafer-level under-fill material, photo-coupler
encapsulating material and others to construct an electronic part. As products obtained
by using a flame-retardant epoxy resin composition of the present invention, there
can be exemplified: IC, LSI, VLSI, thyrister, diode, TSOP (Thin Small Outline Package),
BGA (Ball Grid Array), CSP (Chip Scale/Size Package), COF(Chip On Film/FPC) and others.
[0091] As opto-device material, a flame-retardant epoxy resin composition of the present
invention can be used as encapsulating material for fabrication of LED, a photodiode,
a phototransistor, CCD and others.
(6) Optical Material and Casting Material
[0092] A flame-retardant epoxy resin composition of the present invention is used in an
optical material of an interlayer insulating film for an element of a liquid crystal
display of a segment type, a simple matrix scheme or an active matrix scheme and in
encapsulating material for an element of a liquid crystal display, thus constructing
an electronic part. Furthermore, a flame-retardant epoxy resin composition of the
present invention can be used as a casting material in a coil insulating material
for a relay, a motor, a transformer, an antenna and others.
[0093] Electronic parts described above are subjected to any suitable electrical treatment
and machining to follow and further used in the following applications, which are,
for example, a printer, a computer, a word processor, a key board, a compact information
terminal equipment (PDA), a telephone, a portable telephone, a facsimile, a copier,
an electronic cash register (ECR), a hand held calculator, an electronic notepad,
an electronic dictionary, a card, a holder, an administrative and OA equipment including
stationary, a washer, a refrigerator, a cleaner, a microwave oven, a lighting fixture,
a game machine, an iron, home electrical appliance such as electric foot warmer, a
television set, VTR, a video camera, a radio cassette player, a tape recorder, a mini-disk
player, a CD player, a DVD player, a speaker, AV equipment such as a liquid crystal
display, an EL display, a plasma display and others, a connector, a relay, a capacitor,
a switch, a coil bobbin, a battery, a CCD sensor, an electric wire, a cable, electrical
and electronic parts such as a transformer, a motor, an antenna coil, a deflection
york, a distribution board, a clock and others, and communication equipment such as
non-contact data carrier package system, and others.
[0094] In addition, as other applications of compositions of the present invention, the
compositions are processed into molded articles and incorporated into various types
of construction materials such as an adhesive agent and a paint, and there are exemplified
the following items, which are: materials for an automobile, a vehicle, a ship, an
air plane and building such as various types of packing in and a top cloth of a chair
or a seat; a belt, ceiling and wall boards, a convertible top, an arm rest, a door
trim board, a rear package tray, a carpet, a mat, a sun visor, a wheel cover, a mattress
cover, an air bag, an insulating material, a hand grasp, a hand strap, wire covering
material, electrically insulating material, paint, coating material, facing material,
flooring, a corner wall, a carpet, wall paper, wall facing material, outer facing
material, inner facing material, roofing, a sound insulating board, heat insulating
board, window shade or curtain; and equipment and supplies for daily life and sports
such as clothes, curtain, bed sheets, plywood, a synthetic fiber plate, carpet, a
main entrance mat, a sheet, a bucket, a hose, a container, eyeglasses, a bag, a case,
goggles, a ski, a snowboard, a skateboard, a racket, a tent and a musical instrument.
Examples
[0095] Then, there will be shown synthetic examples, examples and comparative examples and
therewith, detailed description will be given of the present invention. Evaluation
of various aspects of performance was valued as measured according to the following
schemes.
1. Thermal Deformation Temperature
[0096] The temperature was measured in conformity with ASTM D-648 with a load of 1.82 Mpa,
which is used as an index for heat resistance.
2. Flame retardance
[0097] A test piece of a size of 1/16 inch in thickness, 5 inch in length and 0.5 inch in
width was prepared and an evaluation test for flame retardance was applied to the
test piece according to UL-94 standard (Test for Flammability of Plastic Materials
for Parts in Devices and Appliances UL94, Fourth Edition). Definitions of terms and
evaluation criteria used in UL94 are as follows:
[Definitions of Terms]
[0098] Afterflame is that flaming (burning with a flame) of a material after contact of
a flame (after removing an igniter) is sustained.
[0099] An afterflame time is a length of a time during which a material is burning with
a flame after contact of a flame under test conditions.
[0100] Afterglow is that after flaming is over or after contact of a flame unless flaming
occurs, glowing of a material (though not burned with a flame, being kept in a red
heat state serving as an igniter) is sustained as is.
[0101] An afterglow time is a length of a time during which after contact of a flame and/or
after flaming is over, a material is kept in a read heat state serving as an igniter
under test conditions.
t1 is an afterflame time after a first flaming operation,
t2 is an afterflame time after a second flaming operation and
t3 is an afterglow time after the second flaming operation.
[Evaluation Criteria]
[0102] 94 V-0
- (1) afterflame times t1 or t2 of each of test pieces is 10 sec or less,
- (2) the sum (t1 + t2) of afterflame times of 5 test pieces is 50 sec or less,
- (3) the sum (t2 + t3) of an afterflame time and an afterglow time of each of test
pieces after the second flaming operation is 30 sec or less,
- (4) afterflame or afterglow of any test piece does not reach a fixation clamp, and
- (5) a sign of cotton is not ignited by a flaming particle or droppings.
[0103] As thermoplastic resin, thermoset resin and fluororesin, the following resins were
employed:
Epoxy resin: phenol novolak epoxy resin made by DAINIPPON INK KABUSHIKI KAISHA with
a trade name of Epiclon N-770,
Epoxy resin: cresol novolak epoxy resin with an epoxy equivalent of 215 g/eq.,
Phenol resin: a hydroxyl equivalent of 106 g/eq.,
Aromatic polycarbonate resin made by Mitsubishi Engineering Plastics Corp with a trade
name of Iupilon S-2000N
ABS resin made by Mitsui Chemical Corp. with a trade name of Santac UT-61,
and
Polytetrafluoroethylene (PTFE) made by Asahi Glass Co., Ltd. with a trade name of
G-307.
[0104] The following synthetic Examples 1 to 5 are not covered by the claims.
Synthetic Example 1 (synthesis of a raw material phosphazene)
[0105] Into a 10L flask equipped with a reflux condenser, a thermometer, a stirrer, a phosphorous
trichloride dropper and a chlorine gas blowing pipe, 5 L of chlorobenzene, 365 g (6.8
mol) of ammonium chloride and 5.0 g of zinc chloride were put to obtain a mixed dispersion
liquid. The dispersion liquid was heated to a temperature of 130°C and 851 g of phosphorous
trichloride was dropped thereinto at the temperate under reflux at a feed rate of
8.9 g/min over 96 min and 454 g of chlorine gas was simultaneously fed thereinto at
a feed rate of 4.7 g/min over 96 min. After phosphorus trichloride and chlorine gas
were fed, the dispersion liquid was refluxed at temperature of 132°C for another 144
min to complete a reaction. Then, the dispersion liquid was subjected to suction filtration
to remove non-reacted ammonium chloride and a filtrate was distilled under a reduced
pressure of 1.3 to 2.7 hPa at 30 to 40°C to remove chlorobenzene as a distillate and
to obtain 704 g of a reaction product. A yield of the reaction product was 98.1% relative
to the dropped phosphorous trichloride. The reaction product was dissolved into chlorobenzene
and recrystallization was performed to obtain 452 g of a mixture of 76% hexachlorocyclotriphosphazene
and 24% octachlorocyclotetraphosphazene. A residual chlorobenzene solution left after
recrystallization is concentrated to obtain 249 g of cyclic and chain chlorophosphazenes
(a mixture in the general formula (1) with n being 3 to 15, where R
1O- group and R
2O- group are substituted with chlorine atoms). Furthermore, the mixture of hexachlorocyclotriphosphazene
and octachlorocyclotetraphosphazene were recrystallized three times with hexane to
obtain 312 g of hexachlorocyclotriphosphazene of a purity 99.9%.
Synthesis Example 2 (synthesis of phosphazene (A) having amino groups at some but
not all sites)
[0106] Into a 2 L four-necked flask equipped with a reflux condenser, a thermometer, a stirrer
and a dropping funnel, 208.7 g (1.5 mol) of 4-nitrophenol, 141.2 g (1.5 mol) of phenol,
303.6 g (3.0 mol) of triethylamine and 1200 mL of tetrahydrofuran (THF) were put to
obtain a solution. Then, a solution of 116 g (1 unit mol, NPCl
2 is 1 unit) of hexachlorocyclotriphosphazene of a purity 99.9% in 300 mL of THF was
dropped into the THF solution of 4-nitrophenol, phenol and triethylamine over 2 hours
while cooling the solution properly by stirring so that a reaction temperature is
30°C or lower. After the dropping, the reaction was successively continued at room
temperature for another 12 hours while stirring the solution. Then, the reaction was
further performed at a reflux temperature of the solvent for another 6 hours to complete
the reaction. After the reaction ended, a solid (cyclotriphosphazene with a nitrophenoxy
group and a phenoxy group as substitutes in a mixed manner and triethylamine hydrochloric
acid salt) was filtered out and the solid was repeatedly washed with 2 % potassium
hydroxide aqueous solution at 40°C and water sufficient times till water used in the
last washing became neutral. After vacuum drying, there was obtained 272.0 g of a
yellow solid at a yield of 98 %. A residual chlorine quantity is 0.01 % or less and
synthesis of the compound was confirmed by performing
1H- and
31P-NMR analysis. A structure thereof was [NP(OC
6H
4)
0.97(OC
6H
4NO
2)
1.03]
3 as the result of the analysis.
[0107] Into a 1 L four-necked flask, 83.3 g (0.3 unit mol) of a cyclotriphosphazene with
a nitrophenoxy group and a phenoxy group as substitutes in a mixed manner obtained
according to the above process, 5.0 g of active charcoal, 0.5 g of ferric chloride
6 hydrate salt and 600 mL of THF were put and the solution was heated as a pretreatment
under reflux for 10 min. Then, 37.6 g (0.6 mol) of 80 % hydrazine hydrate was added
to the solution, followed by a reaction at a reflux temperature for 8 hours. After
the reaction ended, the charcoal was filtered out and a filtrate was concentrated
and dried to obtain 71.8 g of a light yellow solid at a yield of 97 %. A change from
a nitro group to an amino group was confirmed by performing
1Hand
31P-NMR analysis. A structure thereof was [NP(OC
6R
4)
0.97(OC
6H
4NH
2)
1.03]
3 as the result of the analysis. An amino value (active hydrogen equivalent) of the
compound was measured according to a common method and a result was 120 g/eq.
Synthesis Example 3 (synthesis of phosphazene (B) having amino groups at some but
not all sites)
[0108] A phosphazene having amino groups at some but not all sites in a yellow solid state
was obtained to a weight of 75.2 g (at a total yield of 94%) in a similar process
to Synthesis Example 2 except for use of 87.6 g (0.3 unit mol) of cyclic and chain
clorophosphazenes produced in Synthesis Example 1 (a mixture in the general formula
(1) with n being 3 to 15, where R
1O- group and R
2O- group are substituted with chlorine atoms) instead of hexachlorocyclotriphosphazene
and 299.7 g (1.5 mol) of 4-nitromethylphenol instead of 4-nitophenol. A structure
thereof was [NP(OC
6H
4)
0.97(OC
6H
4CH
2NH
2)
1.03]
3 as the result of
1H- and
31P-NMR analysis. An amino value (active hydrogen equivalent)of the compound was measured
according to a common method and a result was 127 g/eq.
Synthetic Example 4 (synthesis of phosphazene (C) having hydroxy groups at some but
not all sites)
[0109] Into a 2 L four-necked flask equipped with a reflux condenser, a thermometer, a stirrer
and a dropping funnel, 116 g (1 unit mol, NPCl
2 is 1 unit) of a mixture of 82 % hexaclorocyclotriphosphazen and 18 % octaclorocyclotetraphosphazen
and 200mL of THF were put to obtain a solution. Then, a THF solution of 4-methoxyphenol
sodium salt prepared separately (126.5 g (1.1 mol) of 4-methoxyphenol, 23 g (1 g-atom)
of sodium and 400 mL of tetrahydrofuran) was dropped while stirring into the TFT solution
of the mixture of hexachlorocyclotriphosphazene and octaclorocyclotetraphosphazen
over 1 hour. Since there were observed a violent heat release, the reaction was performed
while properly cooling the solution so that a reaction temperature does not exceed
30°C. After the dropping, the reaction was successively continued at 60°C for another
6 hours while stirring the solution. A residual chlorine quantity of a partially substituted
compound obtained by the reaction was at 17.17% and an estimated structure thereof
was [NPCl
0.99(OC
6H
4OCH
3)
1.01]
3,4.
[0110] Then, a THF solution of sodium salt of p-cresol prepared separately (140.6 g (1.3
mol) of p-cresol, 28.8 g (1.2 mol) of sodium and 400 ml of THF) was dropped into the
solution of the partially substituted compound over 1 hour while controlling a reaction
temperature so as to be at 30°C or lower by cooling. Then, the reaction was performed
for 5 hours at room temperature and furthermore for another 3 hours at a reflux temperature
to complete the reaction. After completion of the reaction, THF as a solvent was removed
under a reduced pressure as a distillate, 1 L of toluene was added to the product
to again dissolve and furthermore, 500 mL of water was added to wash the product,
followed by liquid separation. An organic layer was washed with a 5% sodium hydroxide
aqueous solution once and further with a 2% sodium hydroxide aqueous solution once,
and thereafter, washed with a (1 + 9) hydrochloric acid aqueous solution once, washed
with 5% sodium hydrogencarbonate aqueous solution once, and washed with water twice
to cause a pH value of a water layer to be neutral. Then the organic layer was separated
and dehydrated with anhydrous magnesium sulfate, followed by removal of toluene as
distillate to obtain 270.8 g (at a yield of 98%) of a product in a light yellow oily
state. A residual chlorine quantity is 0.01% or lower.
[0111] Into a 2 L four-necked flask, 247.9 g (0.9 unit mol) of a cyclophosphazene with a
4-methoxyphenoxy group and 4-methylphenoxy group as substitutes in a mixed manner
obtained according to the above process and 1040.0 g (9.0 mol) of pyridine hydrochloric
acid salt were put and a temperature of the mixture is gradually raised, followed
by a reaction at a temperature in the range of 205 to 210°C for 1 hour. After cooling
the mixture down to room temperature, 300 mL of water was added thereto to dissolve
a reaction product and excessive pyridine hydrochloric acid salt and further a pH
value of the mixture was adjusted to 6 to 7 with a 20% sodium hydroxide aqueous solution
to prepare a reaction solution. Then, extraction was performed on the reaction solution
with 1 L of ethyl acetate 4 times, thereafter the collected extracts were combined
and washed with 1 L of water saturated with sodium sulfate four times, an organic
layer was separated and the organic layer was dehydrated with anhydrous magnesium
sulfate, followed by removal of ethyl acetate under a reduced pressure as distillate.
Then, the concentrate was dissolved into 300 ml of methanol and the solution was added
into 3 L of water to thereby precipitate a crystal, which process was repeated three
times, followed by vacuum drying of the crystal obtained by the precipitation to obtain
200.0 g (a yield of 85%) of a light yellow crystal. A residual chlorine quantity in
the product is at 0.01% or lower and a quantity of hydroxyl group (OH in %) was quantified
according to acetylation method using acetic anhydride and pyridine described on
page 316 in Analytical Chemistry Handbook, organic version (compiled by Society of
Japan Analytical Chemistry) to obtain a value of 6.5% (the theoretical value of 6.6%). Synthesis of the compound
was confirmed by performing
1H- and
31P-NMR analysis. An estimated structure thereof was [NP(OC
6H
4CH
3)
0.99(OC
6H
4OH)
1.01]
3,4. A hydroxyl group value of the compound was 259 g/eq.
Synthetic Example 5 (synthesis of phosphazene (D) having hydroxyethyl groups at some
but not all sites)
[0112] Into a 2 L four-necked flask equipped with a reflux condenser, a thermometer, a stirrer
and a dropping funnel, 116 g (1 unit mol, NPCl
2 is 1 unit) of a mixture of 82 % hexachlorocyclotriphosphazene and 18 % octaclorocyclotetraphosphazen
and 200mL of THF were put to obtain a solution. Then, a THF solution of phenol sodium
salt prepared separately (103.5 g (1.1 mol) of phenol, 23 g (1 g-atom) of sodium and
400 mL of tetrahydrofuran) was added dropwise while cooling by stirring into the THF
solution of the mixture of hexachlorocyclotriphosphazene and octaclorocyclotetraphosphazen
over 1 hour. After the dropping, the reaction was successively performed at 60°C for
another 6 hours while stirring the solution. A residual chlorine quantity of a partially
substituted compound obtained by the reaction was at 20.16% and an estimated structure
thereof was [NPCl
0.99(OC
6H
4)
1.01]
3,4.
[0113] A THF solution of 4-hydroxyethylphenolate prepared separately (179.6 g (1.3 mol)
of 4-hydroxyethylphenol, 28.8 g (1.2 mol) of sodium and 400 ml of THF) was added dropwise
into the solution of the partially substituted compound over 1 hour while controlling
a reaction temperature so as to be at 30°C or lower by cooling. Then, the reaction
was performed for 5 hours at room temperature and furthermore for another 6 hours
at a reflux temperature to complete the reaction. After completion of the reaction,
THF as a solvent was distilled off under a reduced pressure, then 1 L of toluene was
added to the product to redissolve the product and furthermore 500 mL of water was
added to wash the product, followed by liquid separation. An organic layer was washed
with a 5% sodium hydroxide aqueous solution once and furthermore with a 2% sodium
hydroxide aqueous solution once, and thereafter, washed with a (1 + 9) hydrochloric
acid aqueous solution once, washed with 5% sodium hydrogencarbonate aqueous solution
once, and washed with water twice to cause a pH value of the water layer to be neutral.
Then the organic layer was separated and dehydrated with anhydrous magnesium sulfate,
followed by distillation of toluene to obtain 250.2 g (at a yield of 91%) of a product
in a light yellow oily state. A residual chlorine quantity of the product is 0.01%
or lower and synthesis of the compound was confirmed by performing
1H- and
31P-NMR analysis. A hydroxyl group content was 6.0% (a theoretical value of 6.1%). An
estimated structure thereof was [NP(OC
6H
4CH
2CH
2OH)
0.99(OC
6H
4)
1.01]
3,4. A hydroxyl group value of the compound was 278 g/eq.
Synthetic Example 6 (synthesis of phosphazene (E) having glycidyl groups at some but
not all sites)
[0114] Into a 1 L reactor equipped with a stirrer, a reflux condenser and a thermometer,
78.4 g (0.3 unit mol) of phosphazene (C) having hydroxy groups at some but not all
sites obtained in Synthesis Example 4 and 277.6 (3 mol) of epichlorohydrin were put
to heat and dissolve. Then, a 40% sodium hydroxide aqueous solution (12 g (0.30 mole)
of sodium hydroxide) was added dropwise to the phosphazene solution at a temperature
in the range of 95 to 118°C over 60 min. The reaction was performed at the same temperature
for another 15 min to complete the reaction. After completion of the reaction, epichlorohydrin
and water were distilled off, 1 L of chloroform and 1 L of water were added to the
reaction solution, followed by washing with water twice. An organic layer separated
was dehydrated with anhydrous magnesium sulfate, followed by distillation of chloroform
to obtain 87.7 g of a light yellow solid at a yield of 92%. Synthesis of the compound
was confirmed by performing
1H- and
31P-NMR analysis. An estimated structure thereof was [NP(OC
6H
4CH
3)
0.99(OC
6H
4O
Gly)
1.01]
3.4 (where
Gly indicates a glycidyl group and this applies hereinafter in the description). An epoxy
equivalent of the compound was 315 g/eq.
Synthetic Example 7 (synthesis of phosphazene (F) having glycidyl groups at some but
not all sites)
[0115] A phosphazene having glycidyl groups at some but not all sites in a yellow solid
state was obtained to a weight of 92.2 g (at a yield of 93%) in a similar process
to Synthesis Example 6 except for use of 82.5 g (0.3 unit mol) of a phosphazene (D)
having hydroxyethyl groups at some but not all sites obtained in Synthesis Example
5. Synthesis of the compound was confirmed by performing
1H- and
31P-NMR analysis. An estimated structure thereof was [NP(OC
6H
4CH
2CH
2O
Gly)
0.99(OC
6H
4)
1.01]
3,4. An epoxy equivalent of the compound was 333 g/eq.
[0116] The following synthetic Examples 8 to 10 are not covered by the claims.
Synthetic Example 8 (synthesis of phenoxyphosphazene compound (K))
[0117] Into a 1L four-necked flask equipped with a stirrer, a thermometer and a reflux condenser,
123.0 g (1.3 mol) of phenol was added and further 500 ml of THF was added to form
a homogeneous solution. Then, 27.6 g of metallic sodium was put into the solution
at a temperature of 25°C or lower and thereafter, a temperature of the solution was
raised to 61°C over 1 hour after input of metallic sodium, followed by stirring the
solution at a temperature from 61 to 68°C for 6 hours, thereby preparing a sodium
phenolate solution.
[0118] In parallel to the above reaction, 58.0 g (0.5 unit mol) of a mixture of hexachlorocyclotriphosphazene
and octachlorocyclotetraphosphazene (76% a trimer and 24% a tetramer) were dissolved
into 250mL of THF in a 2 L four-necked flask and the sodium phenolate solution prepared
as described above was added dropwise into the solution of the mixture in a state
being stirred at a temperature of 25°C or lower. After the dropping ended, a reaction
was caused in the mixture solution at a temperature from 71 to 78°C for 15 hours while
stirring. After completion of the reaction, the reaction mixture was concentrated
and further redissolved into 500 ml of toluene, thereafter washed with water, washed
with a 5% sodium hydroxide aqueous solution three times, washed with a 5% hydrochloric
acid aqueous solution, washed with a 5% sodium hydrogencarbonate aqueous solution
and washed with water three times, followed by concentration and drying of the reaction
mixture to obtain 109 g (at a yield of 94%) of a light yellow solid.
[0119] A residual chorine quantity (Hy-Cl) was 0.07% and it was confirmed that the product
(K) was the following compound by performing
1H- and
31P-NMR analysis:
[N = P(-OPh)
2]
3,4.
Synthetic Example 9 (synthesis of phosphazene polymer (G))
[0120] Into a 1L reactor equipped with a stirrer, a reflux condenser and a thermometer,
78.3 g (0.3 unit mol) of a phosphazene (A) having amino groups at some but not all
sites: [NP(OC
6H
4)
0.97(OC
6H
4NH
2)
1.03]
3 obtained in Synthesis Example 2, 105.5 g (0.31 mol) of bisphenol-A diglycidyl ether,
1.0 g of triethanolamine and 700 mL of THF were put and a reaction was performed in
the solution under reflux for 6 hours. After completion of the reaction, the reaction
solution was concentrated and dried to obtain 180.1 g of a yellow solid. An IR analysis
was performed to confirm the absence of a glycidyl group in the product.
Synthetic Example 10 (synthesis of phosphazene polymer (H))
[0121] A phosphazene polymer (H) in a yellow solid state was obtained to a weight of 184.2
g in a similar process to Synthesis Example 9 except for use of 82.5 g (0.3 unit mol)
of a mixture (D) of a cyclotriphosphazene and a cyclotetraphosphazene having a hydroxyethyl
group, [NP(OC
6H
4CH
2CH
2OH)
0.99(OC
6H
4)
1.01]
3.4, obtained in Synthesis Example 5. An IR analysis was performed to confirm the absence
of a glycidyl group in the product.
Synthetic Example 11 (synthesis of phosphazene polymer (I))
[0122] Into a 1L reactor equipped with a stirrer, a reflux condenser and a thermometer,
190.7 g (0.6 unit mol) of a mixture (E) of a cyclotriphosphazene and a cyclotetraphosphazene
each having a glycidyl group, [NP(OC
6H
4CH
3)
0.99(OC
6H
4O-
Gly)
1.01]
3,4, obtained in Synthesis Example 6, 1.0 g of triethanolamine and 700 mL of THF were
put and a reaction was caused in the solution under reflux for 6 hours. After completion
of the reaction, the reaction solution was concentrated and dried to obtain 181.9
g of a yellow solid. An IR analysis was performed to confirm the absence of a glycidyl
group in the product.
Synthetic Example 12 (synthesis of phosphazene polymer (J))
[0123] Into a 1L reactor equipped with a stirrer, a reflux condenser and a thermometer,
99.1 g (0.3 unit mol) of a mixture (F) of a cyclotriphosphazene and a cyclotetraphosphazene
each having a glycidyl group,
[NP(OC
6H
4CH
2CH
2O
Gly)
0.99(OC
6H
4)
1.01]
3,4, obtained in Synthesis Example 7, 28.2 g (0.3 mol) of phenol, 1.0 g of triethanolamine
and 700 mL of THF were put and a reaction was performed in the solution under reflux
for 6 hours. After completion of the reaction ended, the reaction solution was concentrated
and dried to obtain 123.5 g of a yellow solid. An IR analysis was performed to confirm
the absence of a glycidyl group in the product.
[0124] The following Examples 1 to 3 and Comparative Example 1 are not covered by the claims.
Example 1
[0125] N.N'-dimethylformamide was added to 100 parts by weight of phenol novolak epoxy resin,
63 parts by weight of a phosphazene compound (A) prepared in Synthesis Example 2 and
0.2 part by weight of triphenylphosphine to prepare a varnish having a non-volatile
matter concentration of 60%. Using the varnish, 100 parts of glass cloth of 0.18 mm
in thickness made by NITTO BOSEKI CO. LTD. was impregnated with 85 parts of the varnish
as solid matter, and the impregnated glass cloth was dried for 5 min in a drying furnace
at 150°C to fabricate a prepreg of a resin content of 45.9%. Six pieces of prepreg
thus fabricated were superimposed on one another, two electrolytic copper foils of
35 µm in thickness were further superimposed on the top and bottom sides thereof,
the superimposed intermediate was subjected to hot pressure molding at 190°C under
a pressure of 4 Mpa for 120 min to finally obtain a double-sided copper clad laminate
of 1.2 mm in thickness. A flame retardance of the laminate thus obtained was evaluated
according to the UL-94V standard. A soldering heat resistance and a peel strength
were measured in conformity with JIS C 6481, wherein a soldering heat resistance was
evaluated by inspecting whether or not appearance abnormality occurs after moisture
absorption of a test piece kept in boiling water for 2 hours and in addition, immersion
in a solder bath at 260 °C for 120 sec. Compounding recipes and results are shown
in Table 1.
Examples 2 to 5 and Comparative Example 1
[0126] Double-sided copper clad laminates were fabricated in a method similar to that used
in Example 1 except for adoption of the recipes shown in Table 1. From the evaluation
results shown in Table 1, it is found that the laminates of compounding recipes shown
in respective examples are all excellent in flame retardance and moisture resistance.
Table 1
|
example 1 |
example 2 |
example 3 |
example 4 |
example 5 |
comparative example 1 |
phenol novolak resin |
100 |
100 |
100 |
50 |
50 |
100 |
phosphazene compound A |
63 |
|
|
|
|
|
phosphazene compound B |
|
67 |
|
|
|
|
phosphazene compound D |
|
|
146 |
|
|
|
phosphazene compound E |
|
|
|
50 |
|
|
phosphazene compound F |
|
|
|
|
50 |
|
phosphazene compound K |
|
|
|
|
|
70 |
phenol resin |
|
|
|
45 |
44 |
|
tripheaylphos-phme |
0.2 |
0.2 |
0.2 |
0.2 |
0.2 |
0.2 |
phosphorus content (%) |
4.8 |
4.8 |
6.7 |
3.4 |
3.3 |
5.5 |
nitrogen content (%) |
2.2 |
2.1 |
3 |
1.5 |
1.5 |
2.5 |
UL-94V |
V-0 |
V-0 |
V-0 |
V-0 |
V-0 |
V-0 |
soldering heat resistance |
not anomalous |
not anomalous |
not anomalous |
not anomalous |
not anomalous |
peeled |
peel strength (kN/m) |
1.79 |
1.75 |
1.83 |
1.83 |
1.82 |
1.05 |
[0127] The following Example 6 and Comparative Example 2 are not covered by the claims.
Example 6
[0128] An epoxy resin composition of the present invention was produced in a procedure in
which 12 % by weight of a phosphazene compound (D) obtained in Synthesis Example 5,
72 % by weight of fused silica powder, 0.5 % by weight of ester wax and 0.5 % by weight
of a silane coupling agent were added to 15 % by weight of cresol novolak epoxy resin
(with an epoxy equivalent of 215), all the components were mixed at ordinary temperature
and furthermore kneaded at a temperature from 90 to 95°C, followed by cooling and
obtained hard blocks were pulverized.
[0129] The epoxy resin composition is transfer injected into a metal mold heated at 170°C
and hardened therein to fabricate a molded article (an encapsulated article). A water
absorption, a glass transition temperature and moisture resistance were measured on
the molded article and test methods therefor are as follows:
Water Absorption (wt %): an epoxy resin composition of the present invention was transfer
molded to produce a test piece of 50 mm in diameter and 3 mm in thickness, the test
piece was stored in a saturated water vapor atmosphere at 127°C under 2 atm for 24
hours and a water absorption was calculated from a change in weight of the test piece.
Glass Transition Temperature (°C): a test piece same as the test piece for a water
absorption test was post-cured (at 175°C for 8 hours) and thereafter, the test piece
were subjected to measurement of a glass transition temperature with a thermal analyzer.
Moisture Resistance (PCT after immersion in a solder bath): A silicon chip (a test
element) having two or more aluminum wires thereon was adhered to a 42 alloy frame
by using an epoxy resin composition of the present invention and the chip was processed
into a flat package molded article of 5 x 10 x 1.5 (mm) in size by transfer molding
at 175°C for 2 min. The intermediate molded article was post cured at 175°C for 8
hours, followed by a moisture resistance test on the test piece. That is, the flat
package molded article was subjected firstly to moisture absorption by storing in
an atmosphere at 40°C and 90% RH for 100 hours in advance, secondly to an immersion
treatment in a solder bath at 250°C for 10 sec, then PCT was performed on the article
in a saturated water vapor atmosphere at 127°C under 2.5 atm and if wire disconnection
due to corrosion of aluminum occurs on the article in the PCT, the article was evaluated
as defective. A relationship between an elapsed time and a frequency of defective
occurrence in PCT was investigated. The number of samples was 20.
Comparative Example 2
[0130] Molded articles (encapsulated articles) were fabricated to evaluate properties such
as moisture resistance and others in a similar manner to Example 6 except for use
of a phosphazene compound (K) obtained in Synthesis Example 8 instead of a phosphazene
compound (D). Results are shown in Table 2.
Table 2
|
example 6 |
comparative example 2 |
water absorption (%) |
0.03 |
0.49 |
glass transition temperature (°C) |
169 |
161 |
moisture resistance after 40 hours elapses |
0/20 |
4/20 |
after 100 hours elapses |
0/20 |
12/20 |
after 150 hours elapses |
0/20 |
20/20 |
after 200 hours elapses |
0/20 |
- |
[0131] In Example 6 of the present invention, wherein phosphazene compounds having an amino
group, a hydroxy group and a glycidyl group were used, a hot-state hardness was increased,
water absorption was low, an adhesion strength and high temperature storage characteristics
were improved as compared with Comparative Example 2 containing a phenoxyphosphazene
compound. In the examples wherein a flame retardant of the present invention was used,
molded articles were excellent in not only high temperature storage characteristics
but also flame retardance.
[0132] The following Reference Examples 1 and 2 are not covered by the claims.
Reference Example 1
[0133] Fifteen parts of a phosphazene compound (G) of Synthetic Example 9 and 0.5 part of
PTFE were added to a resin composed of 70 parts by weight of aromatic polycarbonate
resin and 30 parts by weight of ABS resin and the components were mixed in a mixer
and thereafter, fused and kneaded using a 25 mm two-roll kneader to obtain a flame-retardant
resin composition.
[0134] The composition was prepared into a test piece of 1/16 inch in thickness by means
of injection molding and the test pieces was subjected to evaluation on flame retardance
on the basis of the test method of UL-94, measurement on a thermal deformation temperature
in conformity with ASTM D-648 and further juicing and mold deposit (MD) phenomena
were observed in molding.
Reference Examples 2 to 4
[0135] Phosphazene compounds (H) to (J) of Synthetic Examples 10 to 12 were used instead
of a phosphazene compound (G) of Synthetic Example 9 and preparation of test pieces
and evaluation thereof were performed in a similar way to Reference Example 1. Results
are shown in Table 3.
[0136] The following Reference Comparative Example 1 and Reference Examples 5 and 6 are
not covered by the claims.
Reference Comparative Example 1
[0137] A phenoxyphosphazene compound (K) of Synthetic Example 8 was used instead of a phosphazene
compound (G) of Synthetic Example 9 and preparation of test pieces and evaluation
thereof were performed in a similar way to Reference Example 1. Results are shown
in Table 3.
Reference Example 5
[0138] Twenty five parts of a phosphazene polymer (G) produced in Synthetic Example 9 were
added to 100 parts of ABS resin and the components were mixed in a mixer and thereafter,
fused and kneaded using a 25 mm two-roll kneader to obtain a flame-retardant resin
composition.
[0139] The composition was prepared into a test piece of 1/16 inch in thickness by means
of injection molding and the test pieces were subjected to evaluation on flame retardance
on the basis of the test method of UL-94 and measurement on a thermal deformation
temperature in conformity with ASTM D-648 and furthermore, juicing and mold deposit
(MD) phenomena were observed in molding. Results are shown in Table 3.
Reference Examples 6 to 8
[0140] Phosphazene compounds (H) to (J) of Synthetic Examples 10 to 12 were used instead
of a phosphazene compound (G) produced in Synthetic Example 9 and preparation of test
pieces and evaluation thereof were performed in a similar way to Reference Example
5. Results are shown in Table 3.
[0141] The following Reference Comparative Example 2 is not covered by the claims.
Reference Comparative Example 2
[0142] A phenoxyphosphazene compound (K) produced in Synthesis Example 8 was used instead
of a phosphazene compound (G) produced in Synthetic Example 9 and preparation of test
pieces and evaluation thereof were performed in a similar way to Reference Example
5. Results are shown in Table 3. Note that the term "Comparative Example" in the tables
is an abbreviation of the term "Reference Comparative Example."
Table 3
|
synthetic resin |
flame retardant |
PTFE part by weight |
UL-94V |
thermal deformation temperature (°C) |
juicing in molding |
MD |
reference example 1 |
PC/ABS |
G |
0.5 |
V-0 |
109 |
absent |
absent |
reference example 2 |
PC/ABS |
H |
0.5 |
V-0 |
106 |
absent |
absent |
reference example 3 |
PC/ABS |
I |
0.5 |
V-0 |
108 |
absent |
absent |
reference example 4 |
PC/ABS |
J |
0.5 |
V-0 |
106 |
absent |
absent |
reference example 5 |
ABS |
G |
0.5 |
V-0 |
82 |
absent |
absent |
referee example 6 |
ABS |
H |
0.5 |
V-0 |
83 |
absent |
absent |
reference example 7 |
ABS |
I |
0.5 |
V-0 |
81 |
absent |
absent |
reference example 8 |
ABS |
J |
0.5 |
V-0 |
83 |
absent |
absent |
Comparative example 1 |
PC/ABS |
K |
0.5 |
V-0 |
98 |
present |
present |
comparative example 2 |
ABS |
K |
0.5 |
V-0 |
78 |
present |
present |
[0143] In such way, Reference Examples 7 and 8 using phosphazene compounds of the present
invention, thermal deformation temperature was raised, neither of juicing and mold
deposit phenomena was recognized as compared with Reference Comparative Examples 1
and 2 containing phenoxyphosphazenes. In all of the examples using flame retardants
of the present invention, any of vaporization, disappearance and bleeding out was
not observed and in addition they are excellent in flame retardance.
[0144] A flame-retardant epoxy resin composition of the present invention was excellent
in heat resistance and moisture resistance.
[0145] Therefore, a molded article obtained by molding a flame-retardant epoxy resin composition
of the present invention has such excellent characteristics and is useful for various
types of products.
[0146] Furthermore, electronic parts such as printed circuit substrate using a flame-retardant
epoxy resin composition of the present invention were excellent in heat resistance
and moisture resistance and, consequently, have high usefulness in industrial aspects.